Pyrazolopyrimidines and the use thereof for controlling harmful organisms

ABSTRACT

This invention relates to novel pyrazolopyrimidines of the formula  
                 
in which  
     R 1 , R 2 , R 3 , X 1  and X 2  are as defined in the disclosure, to a process for preparing these substances and to their use for controlling harmful organisms. This invention further relates to novel intermediates of the formulae  
                 
and to processes for their preparation.

The present invention relates to novel pyrazolopyrimidines, to aplurality of processes for their preparation and to their use forcontrolling harmful organisms. Moreover, the invention relates to novelintermediates and to processes for their preparation.

It is already known that certain pyrazolopyrimidines have fungicidalproperties (compare DE-A 3 130 633 or FR-A 2 794 745). The activity ofthese substances is good; however, at low application rates it issometimes unsatisfactory.

This invention now provides novel pyrazolopyrimidines of the formula

in which

-   -   R¹ represents amino, hydroxyl or represents in each case        optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl,        alkoxy, alkenyloxy, alkinyloxy, cycloalkyloxy, alkylamino,        dialkylamino, alkenylamino, alkinylamino, cyclo-alkylamino,        N-cycloalkyl-N-alkylamino, alkylideneamino or heterocyclyl,    -   R² represents hydrogen or represents in each case optionally        substituted alkyl, alkenyl, alkynyl or cycloalkyl, or    -   R¹ and R² together with the nitrogen atom to which they are        attached form an optionally substituted heterocyclic ring,    -   R³ represents optionally substituted aryl,    -   X¹ represents hydrogen or halogen and    -   X² represents halogen, cyano, nitro, alkyl, haloalkyl,        cycloalkyl, formyl, thiocarbamoyl, alkoxycarbonyl,        alkylcarbonyl, hydroximinoalkyl or alkoximinoalkyl,        and acid addition salts of those compounds of the formula (I),        in which    -   R¹ represents amino.

Depending on the substitution pattern, the compounds according to theinvention may, if appropriate, be present as mixtures of differentpossible isomeric forms, in particular of stereoisomers, such as, forexample, E and Z, threo and erythro and optical isomers, and, ifappropriate, also in the form of tautomers. If R³ carries differentsubstituents on the two atoms adjacent to the point of attachment, thecompounds in question may be present in a particular stereoisomericform, that is, as atropi somers.

Furthermore, it has been found that pyrazolopyrimidines of the formula(I) can be prepared by

a) reacting halopyrazolopyrimidines of the formula

in which

-   -   R³ and X¹ are as defined above,    -   X³ represents halogen, cyano, nitro, alkyl, haloalkyl,        cycloalkyl, thiocarbamoyl, alkoxycarbonyl or alkylcarbonyl and    -   Y¹ represents halogen    -   with amines of the formula        in which    -   R¹ and R² are as defined above,    -   if appropriate in the presence of a diluent, if appropriate in        the presence of a catalyst and if appropriate in the presence of        an acid acceptor,        or

b) reacting pyrazolopyrimidines of the formula (Ia)

in which

-   -   R¹, R², R³ and X¹ are as defined above    -   with diisobutylaluminium hydride in the presence of aqueous        ammonium chloride solution and in the presence of an organic        diluent,    -   or

c) reacting pyrazolopyrimidines of the formula (Ib)

in which

-   -   R¹, R², R³ and X¹ are as defined above    -   with amino compounds of the formula (IV)        H2N—OR⁴   (IV),        in which    -   R⁴ represents hydrogen or alkyl,    -   in the presence of a diluent and if appropriate in the presence        of a catalyst, where the amino compounds of the formula (IV) can        also be employed in the form of their acid addition salts,    -   and, if appropriate, adding an acid to the resulting compounds        of the formula (I), in which    -   R¹ represents amino.

Finally, it has been found that the novel pyrazolopyrimidines of theformula (I) and their acid addition salts are highly suitable forcontrolling harmful organisms. In particular, they have strong actionagainst undesirable microorganisms, such as fungi and bacteria.Moreover, the substances according to the invention also have very goodinsecticidal and nematicidal action.

Surprisingly, the pyrazolopyrimidines of the formula (I) according tothe invention and their acid addition salts have considerably betteractivity against harmful organisms than the constitutionally mostsimilar substances of the prior art with the same direction of action.

The formula (I) provides a general definition of the pyrazolopyrimidinesaccording to the invention.

-   -   R¹ preferably represents hydroxyl, amino, represents alkyl        having 1 to 6 carbon atoms which is optionally substituted by        halogen, cyano, hydroxyl, amino, phenyl, heterocyclyl, alkoxy        having 1 to 4 carbon atoms, alkoxycarbonyl having 1 to 4 carbon        atoms in the alkoxy moiety, alkylamino having 1 to 4 carbon        atoms, dialkylamino having 2 to 8 carbon atoms, cycloalkyl        having 3 to 6 carbon atoms, halocycloalkyl having 3 to 6 carbon        atoms and 1 to 5 halogen atoms, alkylthio having 1 to 4 carbon        atoms, oxo, hydroxyimino and/or alkoximino having 1 to 4 carbon        atoms,        -   represents optionally halogen-, cycloalkyl-, cyano-, phenyl-            and/or heterocyclyl-substituted alkenyl having 2 to 6 carbon            atoms,        -   represents optionally halogen-, cycloalkyl-, cyano-, phenyl-            and/or heterocyclyl-substituted alkynyl having 2 to 6 carbon            atoms,        -   represents optionally cycloalkyl having 3 to 7 carbon atoms            which is optionally substituted by halogen, cycloalkyl,            cyano, haloalkyl having 1 or 2 carbon atoms and 1 to 5            halogen atoms, phenyl and/or heterocyclyl,        -   represents optionally halogen-, cycloalkyl-, cyano-, phenyl-            and/or heterocyclyl-substituted alkoxy having 1 to 7 carbon            atoms,        -   represents optionally halogen-, cycloalkyl-, cyano-, phenyl-            and/or heterocyclyl-substituted alkenyloxy having 2 to 6            carbon atoms,        -   represents optionally halogen-, cycloalkyl-, cyano-, phenyl-            and/or heterocyclyl-substituted alkynyloxy having 2 to 6            carbon atoms,        -   represents optionally halogen-, cycloalkyl-, cyano-, phenyl-            and/or heterocyclyl-substituted cycloalkyloxy having 3 to 7            carbon atoms,        -   represents optionally halogen-, cycloalkyl-, cyano-, phenyl-            and/or heterocyclyl-substituted alkylamino having 1 to 7            carbon atoms,        -   represents optionally halogen-, cycloalkyl-, cyano-, phenyl-            and/or heterocyclyl-substituted dialkylamino having 1 to 7            carbon atoms in each of the alkyl radicals,        -   represents optionally halogen-, cycloalkyl-, cyano-, phenyl-            and/or heterocyclyl-substituted alkenylamino having 2 to 6            carbon atoms,        -   represents optionally halogen-, cycloalkyl-, cyano-, phenyl-            and/or heterocyclyl-substituted alkynylamino having 2 to 6            carbon atoms,        -   represents optionally halogen-, cycloalkyl-, cyano-, phenyl-            and/or heterocyclyl-substituted cycloalkylamino having 3 to            7 carbon atoms,    -   represents optionally halogen-, cycloalkyl-, cyano-, phenyl-        and/or heterocyclyl-substituted N-cycloalkyl-N-alkylamino having        3 to 7 carbon atoms in the cycloalkyl moiety and 1 to 7 carbon        atoms in the alkyl moiety,        -   represents optionally halogen-, cycloalkyl-, cyano-, phenyl-            and/or heterocyclyl-substituted alkylideneamino having 2 to            6 carbon atoms, or        -   represents optionally halogen-, alkyl-, cycloalkyl-, cyano-,            phenyl- and/or heterocyclyl-substituted heterocyclyl having            5 or 6 ring members,        -   where the heterocyclyl radicals mentioned above may be mono-            to trisubstituted by identical or different substituents            from the group consisting of            -   halogen, hydroxy, phenyl, 1,2-dioxyethylene, alkyl                having 1 to 4 carbon atoms, haloalkyl having 1 or 2                carbon atoms and 1 to 5 halogen atoms, alkoxy having 1                to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms,                haloalkoxy having 1 or 2 carbon atoms and 1 to 5 halogen                atoms, haloalkylthio having 1 or 2 carbon atoms and 1 to                5 halogen atoms, where the heterocyclyl radicals                mentioned above are saturated or partially unsaturated,        -   and where the phenyl radicals mentioned above may be mono-            to trisubstituted by identical or different substituents            from the group consisting of            -   halogen, cyano, nitro, amino, hydroxyl, formyl,                carboxyl, carbamoyl, thiocarbamoyl;            -   in each case straight-chain or branched alkyl, alkoxy,                alkylthio, alkylsulphinyl or alkylsulphonyl having in                each case 1 to 6 carbon atoms;            -   in each case straight-chain or branched alkenyl or                alkenyloxy having in each case 2 to 6 carbon atoms;            -   in each case straight-chain or branched haloalkyl,                haloalkoxy, haloalkylthio, haloalkylsulphinyl or                haloalkylsulphonyl having in each case 1 to 6 carbon                atoms and 1 to 13 identical or different halogen atoms;            -   in each case straight-chain or branched haloalkenyl or                haloalkenyloxy having in each case 2 to 6 carbon atoms                and 1 to 13 identical or different halogen atoms;            -   in each case straight-chain or branched alkylamino,                dialkylamino, alkylcarbonyl, alkylcarbonyloxy,                alkoxycarbonyl, alkylsulphonyloxy, hydroximinoalkyl or                alkoximinoalkyl having in each case 1 to 6 carbon atoms                in the individual alkyl moieties;            -   cycloalkyl having 3 to 6 carbon atoms,            -   1,3-propanediyl attached in the 2,3-position,                1,4-butanediyl, methylenedioxy (—O—CH2-O—) or                1,2-ethylenedioxy (—O—CH2-CH2-O—),            -   where these radicals may be mono- or polysubstituted by                identical or different substituents from the group                consisting of halogen, alkyl having 1 to 4 carbon atoms                and haloalkyl having 1 to 4 carbon atoms and 1 to 9                identical or different halogen atoms.    -   R² preferably represents hydrogen,        -   represents alkyl having 1 to 4 carbon atoms which is            optionally substituted by halogen, cycloalkyl having 3 to 6            carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio            having 1 to 4 carbon atoms, oxo, hydroximino and/or            alkoximino having 1 to 4 carbon atoms,        -   represents alkenyl having 2 to 4 carbon atoms which is            optionally substituted by halogen and/or cycloalkyl having 3            to 6 carbon atoms,        -   represents alkynyl having 2 to 4 carbon atoms which is            optonally substituted by halogen and/or cycloalkyl having 3            to 6 carbon atoms or        -   represents cycloalkyl having 3 to 6 carbon atoms which is            optionally substituted by halogen and/or cycloalkyl having 3            to 6 carbon atoms.    -   R¹ and R² also preferably together with the nitrogen atom to        which they are attached represent a 3- to 6-membered        heterocyclic ring which is saturated or partially saturated,        which, in addition to the nitrogen atom already mentioned, may        contain a further heteroatom from the group consisting of        nitrogen, oxygen and sulphur and which may be mono- to        trisubstituted by identical or different substituents from the        group consisting of        -   halogen, hydroxyl, cyano, morpholinyl, amino, a fused phenyl            ring, a methylene or ethylene bridge,        -   alkyl having 1 to 4 carbon atoms,        -   haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or            different halogen atoms;        -   alkylcarbonylamino having 1 to 4 carbon atoms in the alkyl            moiety, dialkylamino having 2 to 8 carbon atoms,        -   alkoxycarbonylamino having 1 to 4 carbon atoms in the alkoxy            moiety,        -   di(alkoxycarbonyl)amino having 2 to 8 carbon atoms in the            alkoxy moieties,        -   hydroxyalkyl having 1 to 4 carbon atoms,        -   alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy            moiety and        -   alkylcarbonyl having 1 to 4 carbon atoms in the alkyl            moiety.    -   R³ preferably represents phenyl which may be mono- to        tetrasubstituted by identical or different substituents from the        group consisting of        -   halogen, cyano, nitro, amino, hydroxyl, formyl, carboxyl,            carbamoyl, thiocarbamoyl;        -   in each case straight-chain or branched alkyl, alkoxy,            alkylthio, alkylsulphinyl or alkylsulphonyl having in each            case 1 to 6 carbon atoms;        -   in each case straight-chain or branched alkenyl or            alkenyloxy having in each case 2 to 6 carbon atoms;        -   in each case straight-chain or branched haloalkyl,            haloalkoxy, haloalkylthio, haloalkylsulphinyl or            haloalkylsulphonyl having in each case 1 to 6 carbon atoms            and 1 to 13 identical or different halogen atoms;        -   in each case straight-chain or branched haloalkenyl or            haloalkenyloxy having in each case 2 to 6 carbon atoms and 1            to 11 identical or different halogen atoms;        -   in each case straight-chain or branched alkylamino,            dialkylamino, alkylcarbonyl, alkylcarbonyloxy,            alkoxycarbonyl, alkylsulphonyloxy, hydroximinoalkyl or            alkoximinoalkyl having in each case 1 to 6 carbon atoms in            the individual alkyl moieties;        -   cycloalkyl having 3 to 6 carbon atoms;        -   1,3-propanediyl attached in the 2,3-position, 1,4-butanediyl            methylenedioxy (—O—CH2-O—) or 1,2-ethylenedioxy            (—O—CH2-CH2-O—), where these radicals may be mono- or            polysubstituted by identical or different substituents from            the group consisting of halogen, alkyl having 1 to 4 carbon            atoms and/or haloalkyl having 1 to 4 carbon atoms and 1 to 9            identical or different halogen atoms.    -   X¹ preferably represents hydrogen, fluorine, chlorine or        bromine.    -   X² preferably represents cyano, fluorine, chlorine, bromine,        iodine, nitro, formyl, haloalkyl having 1 to 4 carbon atoms and        1 to 9 fluorine, chlorine and/or bromine atoms, alkyl having 1        to 4 carbon atoms, cycloalkyl having 3 to 6 carbon atoms,        thiocarbamoyl, alkoxycarbonyl having 1 to 4 carbon atoms in the        alkoxy moiety, alkylcarbonyl having 1 to 4 carbon atoms in the        alkyl moiety, hydroximinoalkyl having 1 to 4 carbon atoms in the        alkyl moiety or represents alkoxyiminoalkyl having 1 to 4 carbon        atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl        moiety.    -   R¹ particularly preferably represents hydroxyl, amino, methyl,        ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl,        n-pentyl, i-pentyl, 1,2-dimethyl-propyl, 2,2-dimethylpropyl,        1,2,2-trimethylpropyl, or    -   R¹ particularly preferably represents methoxymethyl,        2-methoxyethyl, methylthiomethyl, 2-methylthioethyl,        hydroximinomethyl, methoximino-methyl, acetylmethyl,        2-hydroximinopropyl, 2-methoximinopropyl, allyl,        2-methylprop-2-enyl, propargyl, 2,2,2-trifluoroethyl,        1-(trifluoromethyl)-ethyl, 3,3,3-trifluoropropyl,        cyclopropylmethyl,        -   cyclopropyloxy, cyclobutyloxy, cyclopentyloxy,            cyclohexyloxy, difluoromethoxy, trifluoromethoxy,            difluorochloromethoxy, trifluoroethoxy,        -   methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or            t-butylamino, dimethylamino, diethylamino,            trifluoroethylamino, cyclohexylmethylamino,            2-cyanoethylamino, allylamino, 1-cyclopropylethylamino,            cyclopropylamino, cyclobutylamino, cyclopentylamino,            cyclohexylamino, 1-methylethylideneamino,        -   represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,            pyrrolidinyl, piperidinyl, morpholinyl, thiamorpholinyl,            piperazinyl, each of which is        -   optionally mono- or disubstituted by identical or different            substituents from the group consisting of fluorine, chlorine            and methyl, or        -   represents optionally substituted pyridylmethyloxy or            thiazolylmethoxy,        -   or    -   R¹ particularly preferably represents        (2,2-dichlorocyclopropyl)methyl, (2-furyl)-methyl,        (2-tetrahydrofuryl)methyl, (2-tetrahydropyranyl)methyl,        1,3-dioxolan-2-ylmethyl, 1-cyclopropylethyl, benzyloxy,        2,4-dichlorobenzyloxy, 2,6-dichlorobenzyloxy, 2-chlorobenzyloxy,        2-fluorocyclopropyl, 2-hexa-hydropyranyloxy, 2-thienylmethyl,        2-trifluoromethylcyclohexyl, 3-(dimethylamino)propyl,        3,5-bistrifluoromethylcyclohexyl, 3,5-dichloro-benzyloxy,        3-aminopropyl, 3-chlorobenzyloxy, 3-trifluoromethylbenzyloxy,        3-trifluoromethylcyclohexyl, 4-trifluoromethylcyclohexyl,        4-chlorobenzyloxy, 4-fluorobenzyloxy,        4-trifluoromethylbenzyloxy, —C(CH3)2-CF3, —C(CH3)2-CH2-COCH3,        —CH(CH2OH)—COOCH3, —CH(CH3)-CH(O—CH3)2, —CH(CH3)-CH═CH2,        —CH(CH3)-CH2-CH(CH3)2, —CH(CH3)-CH2-O—CH3, —CH(CH3)-CH2-OH,        —CH(CH3)-COOCH3, —CH(CH3)-COO-t-butyl, —CH2-C(CH3)=CH2,        —CH2-CH(OCH3)2, —CH2-CH2-CF3, —CH2-CH2-Cl, —CH2-CH2-CN,        —CH2-CH2-N(CH3)2, —CH2-CH2-N(CH3)2, —CH2-CH2-NH2, —CH2-CHF2,        —CH2-CN, —CH2-COOC2H5, —CH2-COOCH3, i-butoxy, —NH—CH2-CF2-CHF2,        —NH—CH2-CF3, —NH—CH2-CH(CH3)2, methoxy, ethoxy, i-propoxy,        t-butoxy or —O—CH(CH3)-CH2-CH3,        -   where the abovementioned thiazolyl and pyridyl radicals may            be substituted, in the case of thiazolyl mono- or            disubstituted and in the case of pyridyl mono- to            trisubstituted, in each case by identical or different            substituents from the group consisting of fluorine,            chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s-            or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or            t-butoxy, methylthio, ethylthio, n- or i-propylthio,            difluoromethoxy, trifluoromethoxy, difluorochloromethoxy,            trifluoroethoxy, difluoromethylthio,            difluorochloromethylthio, dichlorfluoromethylthio,            trifluoromethylthio and phenyl,        -   and where the benzyloxy radicals mentioned above may be            mono- to trisubstituted in the phenyl moiety by identical or            different substituents from the group consisting of        -   fluorine, chlorine, bromine, cyano, nitro, amino, hydroxyl,            formyl, carboxyl, carbamoyl, thiocarbamoyl, methyl, ethyl,            n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n-            or i-propoxy, methylthio, ethylthio, n- or i-propylthio,            methylsulphinyl, ethylsulphinyl, methylsulphonyl or            ethylsulphonyl, trifluoromethyl, trifluoroethyl,            difluoromethoxy, trifluoromethoxy, difluorochlormethoxy,            trifluoroethoxy, difluoromethylthio,            difluorochloro-methylthio, trifluoromethylthio,            trifluoromethylsulphinyl, trifluoromethyl-sulphonyl,            methylamino, ethylamino, n- or i-propylamino, dimethylamino,            diethylamino, acetyl, propionyl, acetyloxy, methoxycarbonyl,            ethoxycarbonyl, methylsulphonyloxy, ethylsulphonyloxy,            hydroximinomethyl, hydroximino-ethyl, methoximinomethyl,            ethoximinomethyl, methoximinoethyl, ethoximinoethyl,            cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl,        -   1,3-propanediyl attached in the 2,3-position, methylenedioxy            (—O—CH₂—O—) or 1,2-ethylenedioxy (—O—CH₂—CH₂—O—), where            these radicals may be mono- or polysubstituted by identical            or different substituents from the group consisting of            fluorine, chlorine, methyl, ethyl, n-propyl, i-propyl and            trifluoromethyl.    -   R² particularly preferably represents hydrogen, methyl, ethyl,        n- or i-propyl, n-, i-, s- or t-butyl, methoxymethyl,        2-methoxyethyl, methylthiomethyl, 2-methylthioethyl,        hydroximinomethyl, methoximinomethyl, acetylmethyl,        2-hydroxyiminopropyl, 2-methoxyiminopropyl, allyl, propargyl,        2,2,2-trifluoroethyl, 1-(1,1,1-trifluoromethyl)ethyl,        cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or        cyclohexylmethyl.    -   R¹ and R² particularly preferably together with the nitrogen        atom to which they are attached represent 1-pyrrolinyl,        3-pyrrolinyl, pyrrolidinyl, dihydropyridinyl, piperidinyl,        pyrazolinyl, pyrazolidinyl, imidazolinyl, imidiazolidinyl,        1,2-diazinanyl, 1,3-diazinanyl, piperazinyl, oxazolinyl,        oxazolidinyl, isoxazolyl, isoxazolidinyl, tetrahydropyridazinyl,        dihydrooxazinyl, morpholinyl, thiazolinyl, thiazolidinyl or        thiomorpholinyl, where the heterocycles mentioned may be        substituted by        -   fluorine, chlorine, bromine, cyano, nitro, amino, hydroxyl,            formyl, carboxyl, carbamoyl, thiocarbamoyl, methyl, ethyl,            n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n-            or i-propoxy, methylthio, ethylthio, n- or i-propylthio,            methylsulphinyl, ethylsulphinyl, methylsulphonyl or            ethylsulphonyl, trifluoromethyl, trifluoroethyl,            difluoromethoxy, trifluoromethoxy, difluoro-chloromethoxy,            trifluoroethoxy, difluoromethylthio,            difluorochloromethyl-thio, trifluoromethylthio,            trifluoromethyl sulphinyl, trifluoromethyl sulphonyl,            methylamino, ethylamino, n- or i-propylamino, dimethylamino,            diethylamino, acetyl, propionyl, acetyloxa, methoxycarbonyl,            ethoxycarbonyl, methyl-sulphonyloxy, ethylsulphonyloxy,            hydroximinomethyl, hydroximinoethyl, methoximinomethyl,            ethoximinomethyl, methoximinoethyl, ethoximinoethyl,            cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,        -   by a fused phenyl ring or        -   by a methanediyl or ethanediyl bridge,        -   or    -   R¹ and R² particularly preferably together represent a grouping        of the formula

In these groups, the position attached to the nitrogen atom is in eachcase marked by *.

-   -   R³ particularly preferably represents phenyl which is mono- to        trisubstituted by identical or different substituents from the        group consisting of        -   fluorine, chlorine, bromine, cyano, nitro, formyl, methyl,            ethyl, n- or i-propyl, n-, i-, s- or t-butyl, allyl,            propargyl, methoxy, ethoxy, n- or i-propoxy, methylthio,            ethylthio, n- or i-propylthio, methylsulphinyl,            ethylsulphinyl, methylsulphonyl, ethylsulphonyl, allyloxy,            propargyloxy, trifluoromethyl, trifluoroethyl,            difluoromethoxy, trifluoromethoxy, difluorchlormethoxy,            trifluorethoxy, difluoromethylthio,            difluorochloromethylthio, trifluoro-methylthio,            trifluoromethylsulphinyl, trifluoromethylsulphonyl,            trichloro-ethynyloxy, trifluoroethynyloxy, chloroallyloxy,            iodopropargyloxy, methylamino, ethylamino, n- or            i-propylamino, dimethylamino, diethylamino, acetyl,            propionyl, acetyloxy, methoxycarbonyl, ethoxycarbonyl,            hydroximinomethyl, hydroximinoethyl, methoximinomethyl,            ethoximino-methyl, methoximinoethyl, ethoximinoethyl,            cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl,        -   1,3-propanediyl attached in the 2,3-position, methylenedioxy            (—O—CH₂—O—) or 1,2-ethylenedioxy (—O—CH₂—CH₂—O—), where            these radicals may be mono- or polysubstituted by identical            or different radicals from the group consisting of fluorine,            chlorine, methyl, ethyl, n-propyl, i-propyl and/or            trifluoromethyl.    -   X¹ particularly preferably represents hydrogen, fluorine or        chlorine.    -   X² particularly preferably represents cyano, fluorine, chlorine,        bromine, iodine, formyl, trifluoromethyl, methoxycarbonyl,        methylcarbonyl, hydroximinomethyl, methoximinomethyl,        thiocarbamoyl, nitro, methyl, ethyl or cyclopropyl. R³ very        particularly preferably represents 2,4-, 2,5- or        2,6-disubstituted phenyl, or represents 2-substituted phenyl or        represents 2,4,6-trisubstituted phenyl.

A very particularly preferred group are the compounds of the formula(I), in which

-   -   R¹ represents amino, hydroxyl, methyl, ethyl, n-propyl,        i-propyl, n-butyl, i-butyl, s-butyl, t-butyl,        1,2-dimethylpropyl, 1,2,2-trimethylpropyl, 2,2-dimethyl-propyl,        trifluoromethyl, 2,2,2-trifluoromethyl, 2,2-difluoroethyl,        2,2,2-trifluoro-1-methylethyl, 3,3,3-trifluoropropyl,        2,2,2-trifluoro-1,1-dimethyl-ethyl, 3-methyl-butyl, allyl,        2-methyl-prop-2-enyl, 2-methoxyethyl, 2,2-dimethoxyethyl,        cyclopropyl, cyclopentyl, cyclohexyl, 2-fluorocyclopropyl,        2-trifluoromethylcyclohexyl, 3-trifluoromethylcyclohexyl,        4-trifluoromethyl-cyclohexyl, 3,5-di(trifluoromethyl)cyclohexyl,        cyclopropylmethyl, dichloro-cyclopropylmethyl,        1-cyclohexylethyl, 2-furylmethyl, 2-tetrahydrofuryl-methyl,        2-thienylmethyl, 1,3-dioxolan-2-ylmethyl, propargyl,        methoxy-carbonylmethyl, ethoxycarbonylmethyl, 2-aminoethyl,        3-aminopropyl, 2-dimethylaminoethyl, cyanomethyl, 2-cyanoethyl,        2-vinyloxyethyl, pyrrolidinyl, piperidinyl, morpholinyl,        thiomorpholinyl or piperazinyl,    -   R² represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i-,        s- or t-butyl, allyl, propargyl, 2,2,2-trifluoroethyl,        1-(1,1,1-trifluoromethyl)ethyl, cyclopropylmethyl,        cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl or        cyclopropyl or    -   R¹ and R² together with the nitrogen atom to which they are        attached represent pyrrolidinyl, piperidinyl, morpholinyl,        thiomorpholinyl, piperazinyl,        5-methyl-3,6-dihydro-1(2H)-pyridinyl,        5-ethyl-3,6-dihydro-1-(2H)-pyridinyl or        tetrahydro-1-(2H)-pyridazinyl, each of which is optionally mono-        or disubstituted by identical or different substituents from the        group consisting of fluorine, chlorine, bromine, cyano,        hydroxyl, methyl, ethyl, trifluoromethyl, methylcarbonyl,        methylcarbonylamino or methoxycarbonyl, or represent a grouping        of the formula    -   R³ represents phenyl which is mono- to trisubstituted in        positions 2, 4 and/or 6 by fluorine and/or chlorine,    -   or    -   R³ represents 2-trifluoromethylphenyl, 2-chloro-5-nitrophenyl or        2-chloro-4-methoxyphenyl,    -   X¹ represents hydrogen or chlorine and    -   X² represents fluorine, chlorine, bromine, iodine, cyano, nitro,        methyl, cyclopropyl, formyl, thiocarbamoyl or methoximinomethyl.

The radical definitions mentioned above can be combined with one anotheras desired. Moreover, individual definitions may not apply.

Compounds which are preferred according to the invention includeaddition products of acids and those pyrazolopyrimidines of the formula(I), in which

-   -   R¹ represents amino and    -   R², R³, X¹ and X² have the meanings mentioned as being preferred        for these radicals.

The acids which may be added preferably include hydrohalic acids, suchas, for example, hydrochloric acid and hydrobromic acid, in particularhydrochloric acid, furthermore phosphoric acid, nitric acid, mono- andbifunctional carboxylic acids and hydroxycarboxylic acids, such as, forexample, acetic acid, maleic acid, succinic acid, fumaric acid, tartaricacid, citric acid, salicylic acid, sorbic acid and lactic acid, and alsosulfonic acids, such as, for example, p-toluenesulphonic acid,1,5-naphthalenedisulphonic acid, saccharin and thiosaccharin.

The general or preferred radical definitions listed above apply both tothe end products of the formula (I) and, correspondingly, to thestarting materials and intermediates required in each case for thepreparation.

Using 3-cyano-5,7-dichloro-6-(2-chlorophenyl)pyrazolo[1,5-a]pyrimidineand methylethylamine as starting materials, the course of the process(a) according to the invention can be illustrated by the formula schemebelow.

Using3-cyano-5-chloro-6-(2-chloro-4-fluorophenyl)-7-(1,2,2-trimethylpropyl-amino)pyrazolo[1,5a]pyrimidineas starting material and diisobutylaluminium hydride as reactioncomponent, the course of the process (b) according to the invention canbe illustrated by the formula scheme below.

Using3-formyl-5-chloro-6-(2-chloro-4-fluorophenyl)-7-(1,2,2-trimethylpropyl-amino)pyrazolo[1,5a]pyrimidineand methoxyamine hydrochloride as starting materials, the course of theprocess (c) according to the invention can be illustrated by the formulascheme below.

The formula (II) provides a general definition of thehalopyrazolopyrimidines required as starting materials for carrying outthe process (a) according to the invention. In this formula (II), R³ andX¹ preferably have those meanings which have already been mentioned inconnection with the description of the compounds of the formula (I)according to the invention as being preferred for these radicals. Y¹preferably represents fluorine, chlorine or bromine, particularlypreferably fluorine or chlorine.

-   -   X³ preferably represents cyano, fluorine, chlorine, bromine,        iodine, nitro, haloalkyl having 1 to 4 carbon atoms and 1 to 9        fluorine, chlorine and/or bromine atoms, alkyl having 1 to 4        carbon atoms, cycloalkyl having 3 to 6 carbon atoms,        thiocarbamoyl, alkoxycarbonyl having 1 to 4 carbon atoms in the        alkoxy moiety or alkylcarbonyl having 1 to 4 carbon atoms in the        alkyl moiety.    -   X³ particularly preferably represents cyano, fluorine, chlorine,        bromine, iodine, trifluoromethyl, methoxycarbonyl,        methylcarbonyl, thiocarbamoyl, nitro, methyl, ethyl or        cyclopropyl.    -   X³ very particularly preferably represents fluorine, chlorine,        bromine, iodine, cyano, nitro, methyl, cyclopropyl or        thiocarbamoyl.

The halopyrazolopyrimidines of the formula (II) are novel. Thesesubstances, too, are suitable for controlling pests, in particular forcontrolling unwanted microorganisms.

The halopyrazolopyrimidines of the formula (II) can be prepared

by

d) reacting hydroxypyrazolopyrimidines of the formula

in which

-   -   R³ and X³ are as defined above    -   with halogenating agents, if appropriate in the presence of a        diluent,        or

e) reacting dihydroxypyrazolopyrimidines of the formula

in which

-   -   R³ and X³ are as defined above    -   with halogenating agents, if appropriate in the presence of a        diluent.

The formula (V) provides a general definition of thehydroxypyrazolopyrimidines required as starting materials for carryingout the process (d) according to the invention. In this formula, R³ andX³ preferably have those meanings which have already been mentioned inconnection with the description of the compounds of the formulae (I) and(II) as being preferred for these radicals.

The hydroxypyrazolopyrimidines of the formula (V), too, have hithertonot been disclosed. They can be prepared by

f) reacting acrylic acid esters of the formula

in which

-   -   R³ is as defined above,    -   R⁵ represents alkyl and    -   Y² represents alkoxy or dialkylamino,    -   with aminopyrazoles of the formula        in which    -   X³ is as defined above,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of a strong base.

The formula (VII) provides a general definition of the acrylic acidesters required as starting materials for carrying out the process (f)according to the invention. In this formula, R³ preferably has thosemeanings which have already been mentioned in connection with thedescription of the substances of the formula (I) according to theinvention as being preferred for this radical. R⁵ preferably representsalkyl having 1 to 4 carbon atoms, particularly preferably methyl orethyl. Y² preferably represents alkoxy having 1 to 4 carbon atoms orrepresents dialkylamino having 1 to 4 carbon atoms in each alkyl group.Particularly preferably, Y² represents methoxy, ethoxy or representsdimethylamino.

The acrylic acid esters of the formula (VII) are known or can beprepared by known methods (cf. EP-A 0 165 448).

The formula (VIII) provides a general definition of the aminopyrazolesrequired as reaction components for carrying out the process (f)according to the invention. In this formula, X³ preferably has thosemeanings which have already been mentioned in connection with thedescription of the substances of the formula (II) according to theinvention as being preferred for this substituent.

The aminopyrazoles of the formula (VIII) are known or can be prepared byknown methods (cf. Tetrahedron Lett. 21, 2029-2031 (1967); Liebigs Ann.Chem. 707, 141-146 (1967), Monatsh. Chem. 1998, 1329 (12), 1313-1318)and J. Med. Chem. 25 (1982), 239 ff).

The formula (VI) provides a general definition of thedihydroxypyrazolopyrimidines required as starting materials for carryingout the process (e) according to the invention. In this formula, R³ andX³ preferably have those meanings which have already been mentioned inconnection with the description of the substances of the formulae (I)and (II) according to the invention as being preferred for theseradicals.

The dihydroxypyrazolopyrimidines of the formula (VI), too, have hithertonot been disclosed. They can be prepared by

g) reacting malonic esters of the formula

in which

-   -   R³ is as defined above and    -   R⁶ represents alkyl,    -   with aminopyrazoles of the formula        in which    -   X³ is as defined above,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of a strong base.

The formula (IX) provides a general definition of the malonic estersrequired as starting materials for carrying out the process (g)according to the invention. In this formula, R³ preferably has thosemeanings which have already been mentioned in connection with thedescription of the substances of the formula (I) according to theinvention as being preferred for this radical. R⁶ preferably representsalkyl having 1 to 4 carbon atoms, particularly preferably methyl orethyl.

The malonic esters of the formula (IX) are known or can be prepared byknown methods (cf. U.S. Pat. No. 6,156,925).

Suitable diluents for carrying out the processes (f) and (g) are allcustomary inert organic solvents. Preference is given to usingaliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether,hexane, heptane, cyclohexane, methylcyclo-hexane, benzene, toluene,xylene or decalin; halogenated hydrocarbons, such as chlorobenzene,dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride,dichloroethane or trichloroethane; ethers, such as diethyl ether,diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane,tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole;nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile orbenzonitrile; amides, such as N,N-dimethyl-formamide,N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone orhexamethylphosphoric triamide; esters, such as methyl acetate or ethylacetate; sulphoxides, such as dimethyl sulphoxide; sulphones, such assulpholane; alcohols, such as methanol, ethanol, n- or i-propanol, n-,i-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol,methoxyethanol, diethylene glycol monomethyl ether, diethylene glycolmonoethyl ether; amines, such as tri-n-butylamine; or carboxylic acids,such as acetic acid.

Suitable strong bases for carrying out the processes (f) and (g)according to the invention are, preferably, alkaline earth metal oralkali metal hydrides or alkoxides and also alkali metal amides. Sodiumhydride, sodium amide, sodium methoxide, sodium ethoxide and potassiumtert-butoxide may be mentioned by way of example.

The processes (f) and (g) according to the invention and also the otherprocesses according to the invention are generally carried out underatmospheric pressure. However, it is also possible to operate underelevated pressure or—unless highly volatile reaction components arepresent—under reduced pressure.

When carrying out the processes (f) and (g) according to the invention,the reaction temperatures can in each case be varied within a relativelywide range. In the absence of bases, the processes are generally carriedout at temperatures between 100° C. and 250° C., preferably between 120°C. and 200° C. If bases are present, the processes are generally carriedout at temperatures between 20° C. and 120° C., preferably between 20°C. and 80° C.

When carrying out the process (f) according to the invention, in general1 to 15 mol, preferably 1 to 8 mol, of aminopyrazole of the formula(VIII) are employed per mole of acrylic acid ester of the formula (VII).Work-up is carried out by customary methods.

When carrying out the process (g) according to the invention, in general1 to 15 mol, preferably 1 to 8 mol, of aminopyrazole of the formula(VIII) are employed per mole of malonic ester of the formula (IX).Work-up is carried out by customary methods.

Suitable halogenating agents for carrying out the processes (d) and (e)according to the invention are in each case all customary reagentssuitable for exchanging hydroxyl groups attached to carbon for halogen.Preference is given to using phosphorus trichloride, phosphorustribromide, phosphorus pentachloride, phosphorus oxychloride, phosgene,thionyl chloride, thionyl bromide or mixtures thereof. The correspondingfluoro compounds of the formula (II) can be prepared from the chloro orbromo compounds by reaction with potassium fluoride.

Suitable diluents for carrying out the processes (d) and (e) accordingto the invention are in each case all organic solvents customary forsuch halogenations. Preference is given to using aliphatic, alicyclic oraromatic hydrocarbons, such as petroleum ether, hexane, heptane,cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin;halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene,dichloromethane, chloroform, carbon tetrachloride, dichloroethane ortrichlorethane.

However, the diluent used can also be the halogenating agent itself or amixture of halogenating agent and one of the diluents mentioned.

When carrying out the processes (d) and (e) according to the invention,the reaction temperatures can in each case be varied within a relativelywide range. In general, the processes are carried out at temperaturesbetween 20° C. and 150° C., preferably between 40° C. and 120° C.

When carrying out the processes (d) and (e) according to the invention,in each case an excess of halogenating agent is used per mole ofhydroxypyrazolopyrimidine of the formula (V) anddihydroxypyrazolopyrimidine of the formula (VI), respectively. Work-upis in each case carried out by customary methods.

The formula (III) provides a general definition of the amines furtherrequired as starting materials for carrying out the process (a)according to the invention. In this formula, R¹ and R² preferably havethose meanings which have already been mentioned in connection with thedescription of the compounds of the formula (I) according to theinvention as being preferred for R¹ and R².

Some of the amines of the formula (III) are known.

Amines of the formula

in which

-   -   R¹ represents isobutyl, 2-methoxyethyl or represents        are novel.

The amines of the formula (IIIa) can be prepared by

h) reacting, in a first step, ethyl N-methoxycarbamate of the formula

with halogen compounds of the formulaR⁷—X⁴   (XI),in which

-   -   R⁷ is as defined above and    -   X⁴ represents bromine or iodine    -   in the presence of a base or in the presence of a diluent and        reacting the resulting carbamates of the formula        in which    -   R⁷ is as defined above,    -   in a second step with potassium hydroxide in the presence of        ethanol and water.

Amines of the formula

in which

-   -   R⁷ is as defined above    -   are also novel.

The amines of the formula (IIIb) can be prepared by

i) reacting, in a first step, ethyl N-hydroxy-N-methylcarbamate of theformula

with halogen compounds of the formulaR⁷—X⁴   (XI),in which

-   -   R⁷ and X⁴ are as defined above    -   in the presence of a base and in the presence of a diluent and        reacting the resulting carbamates of the formula        in which    -   R⁷ is as defined above    -   in a second step with potassium hydroxide in the presence of        ethanol and water.

Trifluoroisopropylamines of the formula

in which

-   -   R⁸ represents methyl, ethyl or propyl        are also novel.

The trifluoroisopropylamines of the formula (IIIc) can be prepared by

j) reacting, in a first step, ethyl N-trifluoroisopropylcarbamate of theformula

with halogen compounds of the formulaR⁸—X⁴   (XVI)in which

-   -   R⁸ and X⁴ are as defined above    -   in the presence of a base and in the presence of a diluent and        reacting the resulting carbamates of the formula        in which    -   R⁸ is as defined above,    -   in a second step with potassium hydroxide in the presence of        ethanol and water.

Finally, the 3-trifluoromethyl-3-aminopropene of the formula

is also novel.

The 3-trifluoromethyl-3-aminopropene of the formula (III-4) can beprepared by

k) reacting the carbamate of the formula

with aqueous hydrochloric acid.

The compounds of the formulae (X), (XI), (XIII), (XV), (XVI) and (XVIII)required as starting materials for carrying out the processes (h)-(j)are known or can be prepared by known methods.

Suitable acid acceptors for carrying out the first step of the processes(h), (i) and (j) according to the invention are in each case allinorganic and organic acid acceptors customary for such reactions.

Preference is given to using alkaline earth metal or alkali metalhydrides, hydroxides, amides, alkoxides, acetates, carbonates orbicarbonates, such as, for example, sodium hydride, sodium amide, sodiummethoxide, sodium ethoxide, potassium tert-butoxide, sodium hydroxide,potassium hydroxide, sodium acetate, potassium acetate, calcium acetate,sodium carbonate, potassium carbonate, potassium bicarbonate and sodiumbicarbonate, and furthermore ammonium compounds, such as ammoniumhydroxide, ammonium acetate and ammonium carbonate. Suitable organicbases which may be mentioned are: tertiary amines, such astrimethylamine, triethyl amine, tributyl amine, N,N-dimethyl aniline,N,N-dimethylbenzylamine, pyridine, N-methylpiperidine,N-methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane(DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

Suitable diluents for carrying out the first step of the processes (h),(i) and (j) are in each case all customary inert organic solvents.Preference is given to using ethers, such as diethyl ether, dioxane,tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole;amides, such as N,N-dimethylformamide, N,N-dimethylacetamide,N-methylformanilide or N-methylpyrrolidone; sulphones, such assulpholane; alcohols, such as methanol, ethanol, isopropanol,tert-butanol, n-butanol.

When carrying out the first step of the processes (h), (i) and (j), thereaction temperatures can in each case be varied within a relativelywide range. In general, the first step is carried out at temperaturesbetween 0° C. and 150° C., preferably between 10° C. and 100° C.

The first step of the processes (h), (i) and (j) is in each casegenerally carried out under atmospheric pressure. However, it is alsopossible to operate under elevated pressure or, if no low-boilingcomponents are involved in the reaction, under reduced pressure.

For carrying out the first step of the processes (h), (i) and (j),

-   -   in general from 0.5 to 15 mol, preferably from 1 to 5 mol, of        halogen compound of the formula (XI) are employed per mole of        ethyl N-methoxycarbamate of the formula (X), or    -   in general from 0.5 to 15 mol, preferably from 1 to 5 mol, of        halogen compound of the formula (XI) are employed per mole of        ethyl N-hydroxy-N-methylcarbamate of the formula (XIII), or    -   in general from 0.5 to 15 mol, preferably from 1 to 5 mol, of        halogen compound of the formula (XVI) are employed per mole of        ethyl N-trifluoroisopropyl-carbamate of the formula (XV).

Work-up is in each case carried out by customary methods, for example byextraction and subsequent drying or by precipitation with subsequentfiltration and drying. Any impurities that may still be present can beremoved by customary methods.

The compounds of the formulae (XI), (XIV) and (XVII) obtained asintermediates when carrying out the first step of the processes (h), (i)and (j) are novel.

When carrying out the second step of processeses (h), (i) and (j), thereaction temperatures can also in each case be varied within arelatively wide range. In general, the second step is carried out attemperatures between 0° C. and 100° C., preferably between 10° C. and80° C.

The second step of the processes (h), (i) and (j), too, is generally ineach case carried out under atmospheric pressure. However, again it isin each case also possible to operate under elevated pressure or, unlessthe products to be isolated have very low boiling points, under reducedpressure.

When carrying out the second step of the processes (h), (i) and (j), ineach case up to 10 mol of potassium hydroxide are employed per mole of acompound of the formula (XII), (XIV) or (XVII). Work-up is carried outby customary methods. Here, the amines are generally expedientlyisolated in the form of their salts by adding acid, preferably aqueoushydrochloric acid.

When carrying out the process (k), the reaction temperatures canlikewise be varied within a relatively wide range. In general, theprocess is carried out a temperatures between 10° C. and 150° C.,preferably at reflux temperature.

The process (k) is generally carried out under atmospheric pressure.However, it is also possible to operate under elevated pressure.

When carrying out the process (k), an excess, preferably up to 10 mol,of aqueous hydrochloric acid is employed per mole of carbamate of theformula (XVM). Work-up is again carried out by customary methods.

Suitable diluents for carrying out the process (a) according to theinvention are all customary inert organic solvents. Preference is givento using aliphatic, alicyclic or aromatic hydrocarbons, such aspetroleum ether, hexane, heptane, cyclohexane, methylcyclohexane,benzene, toluene, xylene or decalin; halogenated hydrocarbons, such aschlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbontetrachloride, dichloroethane or trichloroethane; ethers, such asdiethyl ether, diisopropyl ether, methyl t-butyl ether, dioxane,tetrahydrofuran, 1,2-dimethoxy-ethane or 1,2-diethoxyethane; amides,such as N,N-dimethylformamide, N,N-dimethylacetamide orN-methylpyrrolidone; esters, such as methyl acetate or ethyl acetate;sulphoxides, such as dimethyl sulphoxide; sulphones, such as sulpholane.

Suitable catalysts for carrying out the process according to theinvention are all reaction accelerators customary for such reactions.Preference is given to using alkali metal fluorides, such as potassiumfluoride or caesium fluoride.

Suitable acid acceptors for carrying out the process (a) according tothe invention are all acid binders customary for such reactions.Preference is given to using ammonia and also tertiary amines, such astrimethylamine, triethylamine, tributylamine, N,N-dimethylaniline,N,N-dimethylbenzylamine, pyridine, N-methylpiperidine,N-methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane(DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

When carrying out the process (a) according to the invention, thereaction temperatures can be varied within a relatively wide range. Ingeneral, the process is carried out at temperatures between 0° C. and150° C., preferably at temperatures between 0° C. and 80° C.

When carrying out the process (a) according to the invention, in generalfrom 0.5 to 10 mol, preferably from 0.8 to 2 mol, of amine of theformula (III) are employed per mole of halopyrazolopyrimidine of theformula (II). Work-up is carried out by customary methods.

The formula (Ia) provides a general definition of thepyrazolopyrimidines required as starting materials for carrying out theprocess (b) according to the invention. In this formula, R¹, R², R³ andX¹ preferably have those meanings which have already been mentioned inconnection with the description of the subtances of the formula (I)according to the invention as being preferred for these radicals.

The pyrazolopyrimidines of the formula (Ia) are substances according tothe invention which can be prepared by the process (a) according to theinvention.

Suitable diluents for carrying out the process (b) according to theinvention are all customary inert organic solvents. Preference is givento using aliphatic or aromatic, optionally halogenated hydrocarbons,such as toluene, dichloromethane, chloroform or carbon tetrachloride.

When carrying out the process (b) according to the invention, thereaction temperatures can be varied within a certain range. In general,the process is carried out at temperatures between −80° C. and +20° C.,preferably between −60° C. and +10° C.

In general, the process (b) according to the invention is carried outunder atmospheric pressure. However, it is also possible to operateunder elevated pressure.

When carrying out the process (b) according to the invention, in generalan equivalent amount or else an excess, preferably from 1.1 to 1.2 mol,of diisobutylaluminium hydride are employed per mole ofpyrazolopyrimidine of the formula (Ia), and an excess of aqueousammonium chloride solution is then added. Work-up is carried out bycustomary methods. In general, the reaction mixture is acidified, theorganic phase is separated off, the aqueous phase is extracted with anorganic solvent which is poorly water-miscible and the combined organicphases are washed, dried and concentrated under reduced pressure.

The formula (Ib) provides a general definition of thepyrazolopyrimidines required as starting materials for carrying out theprocess (c) according to the invention. In this formula, R¹, R², R³ andX¹ preferably have those meanings which have already been mentioned inconnection with the description of the substances of the formula (I)according to the invention as being preferred for these radicals.

The pyrazolopyrimidines of the formula (Ib) are substances according tothe invention which can be prepared by the process (b) according to theinvention.

The formula (IV) provides a general definition of the amino compoundsrequired as reaction components for carrying out the process (c)according to the invention. In this formula, R⁴ preferably representshydrogen or alkyl having 1 to 4 carbon atoms, particularly preferablyhydrogen, methyl or ethyl.

Suitable reaction components include acid addition salts, preferablyhydrogen chloride addition salts of amino compounds of the formula (IV).

Both the amino compounds of the formula (IV) and their acid additionsalts are known or can be prepared by known methods.

Suitable diluents for carrying out the process (c) according to theinvention are all customary inert organic solvents. Preference is givento using alcohols, such as methanol, ethanol, n-propanol or isopropanol.

Suitable catalysts for carrying out the process (c) according to theinvention are all reaction accelerators customary for such reactions.Preference is given to using acidic or basic catalysts, such as, forexample, weak basic ion exchangers commercially available under the nameAmberlyst A-21®.

When carrying out the process (c) according to the invention, thereaction temperatures can be varied within a certain range. In general,the process is carried out at temperatures between 0° C. and 80° C.,preferably between 10° C. and 60° C.

In general, the process (c) according to the invention is carried outunder atmospheric pressure. However, it is also possible to operateunder elevated pressure.

When carrying out the process (c) according to the invention, in generalan equivalent amount or an excess, preferably between 1.1 and 1.5 mol,of the amino compound of the formula (IV) or an acid addition saltthereof is employed per mole of pyrazolopyrimidine of the formula (Ib).Work-up is carried out by customary methods. In general, the reactionmixture is, if required, filtered and then concentrated and purified.

Preferred acids for preparing acid addition salts of pyrazolopyrimidinesof the formula (I) are those acids which have already been mentioned aspreferred acids in connection with the description of the acid additionsalts according to the invention.

The acid addition salts of the compounds of the formula (I) can beobtained in a simple manner by customary methods for forming salts, forexample by dissolving a compound of the formula (I) in a suitable inertsolvent and adding the acid, for example hydrochloric acid, and they canbe isolated in a known manner, for example by filtering off and, ifappropriate, be purified by washing with an inert organic solvent.

The active compounds according to the invention are suitable forcontrolling animal pests, in particular insects, arachnids andnematodes, which are encountered in agriculture, in forestry, in theprotection of stored products and of materials, and in the hygienesector, and have good plant tolerance and favourable toxicity towarm-blooded animals. They may preferably be employed as plantprotection agents. They are active against normally sensitive andresistant species and against all or some stages of development. Theabovementioned pests include:

From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus andScutigera spp.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Acheta domesticus,Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp. andSchistocerca gregaria.

From the order of the Blattaria, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae, Blattella germanica.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp.

From the order of the Phthiraptera, for example, Pediculus humanuscorporis, Haematopinus spp., Linognathus spp., Trichodectes spp. andDamalinia spp.

From the order of the Thysanoptera, for example, Hercinothripsfemoralis, Thrips tabaci, Thrips palmi and Frankliniella occidentalis.

From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosomalanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp.,Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi,Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecaniumcomi, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens,Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psyllaspp.

From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padelia, Plutella xylostella, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Mamestra brassicae, Panolisflammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pornella, Pierisspp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleriamellonella, Tineola bisselliella, Tinea pellionella, Hofmannophilapseudospretella, Cacoecia podana, Capua reticulana, Choristoneurafumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana,Cnaphalocerus spp., Oulema oryzae.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedoncochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachnavarivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp.,Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogodermaspp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp.,Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha,Amphimallon solstitialis, Costelytra zealandica and Lissorhoptrusoryzophilus.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae,Tipula paludosa, Hylemyia spp. and Liriomyza spp.

From the order of the Siphonaptera, for example, Xenopsylla cheopis andCeratophyllus spp.

From the class of the Arachnida, for example, Scorpio maurus,Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp.,Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora,Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp.,Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemusspp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.,Hemitarsonemus spp., Brevipalpus spp.

The phytoparasitic nematodes include, for example, Pratylenchus spp.,Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans,Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp.,Longidorus spp., Xiphinema spp., Trichodorus spp., Bursaphelenchus spp.

The active compounds can be used with particularly good results forcontrolling plant-damaging insects, such as, for example, against thecaterpillars of the diamondback moth (Plutella maculipennis).

The substances according to the invention also have potent microbicidalactivity and can be employed for controlling undesirable microorganisms,such as fungi and bacteria, in crop protection and in the protection ofmaterials.

Fungicides can be employed in crop protection for controllingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

Bactericides can be employed in crop protection for controllingPseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceaeand Streptomycetaceae.

Some pathogens causing fungal and bacterial diseases which come underthe generic names listed above may be mentioned as examples, but not byway of limitation:

Xanthomonas species, such as, for example, Xanthomonas campestris pv.oryzae;

Pseudomonas species, such as, for example, Pseudomonas syringae pv.lachrymans;

Erwinia species, such as, for example, Erwinia amylovora;

Pythium species, such as, for example, Pythium ultimum;

Phytophthora species, such as, for example, Phytophthora infestans;

Pseudoperonospora species, such as, for example, Pseudoperonosporahumuli or Pseudoperonospora cubensis;

Plasmopara species, such as, for example, Plasmopara viticola;

Bremia species, such as, for example, Bremia lactucae;

Peronospora species, such as, for example, Peronospora pisi or P.brassicae;

Erysiphe species, such as, for example, Erysiphe graminis;

Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;

Podosphaera species, such as, for example, Podosphaera leucotricha;

Venturia species, such as, for example, Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres or P.graminea (conidia form: Drechslera, syn: Helminthosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus(conidia form: Drechslera, syn: Helminthosporium);

Uromyces species, such as, for example, Uromyces appendiculatus;

Puccinia species, such as, for example, Puccinia recondita;

Sclerotinia species, such as, for example, Sclerotinia sclerotiorum;

Tilletia species, such as, for example, Tilletia caries;

Ustilago species, such as, for example, Ustilago nuda or Ustilagoavenae;

Pellicularia species, such as, for example, Pellicularia sasakii;

Pyricularia species, such as, for example, Pyricularia oryzae;

Fusarium species, such as, for example, Fusarium culmorum;

Botrytis species, such as, for example, Botrytis cinerea;

Septoria species, such as, for example, Septoria nodorum;

Leptosphaeria species, such as, for example, Leptosphaeria nodorum;

Cercospora species, such as, for example, Cercospora canescens;

Alternaria species, such as, for example, Alternaria brassicae; and

Pseudocercosporella species, such as, for example, Pseudocercosporellaherpotrichoides.

The active compounds according to the invention also have very goodfortifying action in plants. Accordingly, they can be used formobilizing the defences of the plant against attack by unwantedmicroorganisms.

In the present context, plant-fortifying (resistance-inducing)substances are to be understood as meaning those substances which arecapable of stimulating the defence system of plants such that, when thetreated plants are subsequently inoculated with unwanted microorganisms,they show substantial resistance against these mircroorganisms.

In the present case, unwanted microorganisms are to be understood asmeaning phytopathogenic fungi, bacteria and viruses. Accordingly, thesubstances according to the invention can be used to protect plants fora certain period after the treatment against attack by the pathogensmentioned. The period for which protection is provided generally extendsover 1 to 10 days, preferably 1 to 7 days, after the treatment of theplants with the active compounds.

The fact that the active compounds according to the invention are welltolerated by plants at the concentrations required for controlling plantdiseases permits the treatment of above-ground parts of plants, ofpropagation stock and seeds, and of the soil.

The active compounds according to the invention can be used withparticularly good results for controlling cereal diseases, such as, forexample, against Fusarium species, diseases in viticulture and fruit andvegetable growing, such as, for example, against Botrytis, Venturia andAlternaria species, or rice diseases, such as, for example, againstPyricularia species.

The active compounds according to the invention are also suitable forincreasing the yield of crops. In addition, they show reduced toxicityand are well tolerated by plants.

If appropriate, the compounds according to the invention can, at certainconcentrations and application rates, also be used as herbicides and forinfluencing plant growth. If appropriate they can also be employed asintermediates and precursors for the synthesis of other activecompounds.

Plants and plant parts can be treated with the active compoundsaccording to the invention. Plants are to be understood as meaning inthe present context all plants and plant populations such as desired andundesired wild plants or crop plants (including naturally occurring cropplants). Crop plants can be plants which can be obtained by conventionalplant breeding and optimization methods or by biotechnological andrecombinant methods or by combinations of these methods, including thetransgenic plants and inclusive of the plant cultivars protectable ornot protectable by plant breeders' rights. Plant parts are to beunderstood as meaning all parts and organs of plants above and below theground, such as shoot, leaf, flower and root, examples which may bementioned being leaves, needles, stalks, stems, flowers, fruit bodies,fruits, seeds, roots, tubers and rhizomes. The plant parts also includeharvested material, and vegetative and generative propagation materialfor example cuttings, tubers, rhizomes, offsets and seeds.

Treatment of the plants and plant parts with the active compoundsaccording to the invention is carried out directly or by allowing thecompounds to act on their surroundings, environment or storage space bythe customary treatment methods, for example by immersion, spraying,evaporation, fogging, scattering, painting on and, in the case ofpropagation material, in particular in the case of seeds, also byapplying one or more coats.

In the protection of materials, the compounds according to the inventioncan be employed for protecting industrial materials against infectionwith and destruction by undesired microorganisms.

Industrial materials in the present context are understood as meaningnon-living materials which have been prepared for use in industry. Forexample, industrial materials which are intended to be protected byactive compounds according to the invention from microbial change ordestruction can be adhesives, sizes, paper and board, textiles, leather,wood, paints and plastic articles, cooling lubricants and othermaterials which can be infected with or destroyed by microorganisms.Parts of production plants, for example cooling-water circuits, whichmay be impaired by the proliferation of microorganisms may also bementioned within the scope of the materials to be protected. Industrialmaterials which may be mentioned within the scope of the presentinvention are preferably adhesives, sizes, paper and board, leather,wood, paints, cooling lubricants and heat-transfer liquids, particularlypreferably wood.

Microorganisms capable of degrading or changing the industrial materialswhich may be mentioned are, for example, bacteria, fungi, yeasts, algaeand slime organisms. The active compounds according to the inventionpreferably act against fungi, in particular moulds, wood-discolouringand wood-destroying fungi (Basidiomycetes), and against slime organismsand algae.

Microorganisms of the following genera may be mentioned as examples:

Alternaria, such as Altemaria tenuis,

Aspergillus, such as Aspergillus niger,

Chaetomium, such as Chaetomium globosum,

Coniophora, such as Coniophora puetana,

Lentinus, such as Lentinus tigrinus,

Penicillium, such as Penicillium glaucum,

Polyporus, such as Polyporus versicolor,

Aureobasidium, such as Aureobasidium pullulans,

Sclerophoma, such as Sclerophoma pityophila,

Trichoderma, such as Trichoderma viride,

Escherichia, such as Escherichia coli,

Pseudomonas, such as Pseudomonas aeruginosa, and

Staphylococcus, such as Staphylococcus aureus.

Depending on their particular physical and/or chemical properties, theactive compounds can be converted into the customary formulations, suchas solutions, emulsions, suspensions, powders, foams, pastes, granules,aerosols and microencapsulations in polymeric substances and in coatingcompositions for seeds, and ULV cool and warm fogging formulations.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurfactants, that is emulsifiers and/or dispersants, and/or foamformers. If the extender used is water, it is also possible to employ,for example, organic solvents as auxiliary solvents. Essentially,suitable liquid solvents are: aromatics such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics or chlorinated aliphatichydrocarbons such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons such as cyclohexane or paraffins, forexample petroleum fractions, alcohols such as butanol or glycol andtheir ethers and esters, ketones such as acetone, methyl ethyl ketone,methyl isobutyl ketone or cyclohexanone, strongly polar solvents such asdimethylformamide and dimethyl sulphoxide, or else water. Liquefiedgaseous extenders or carriers are to be understood as meaning liquidswhich are gaseous at standard temperature and under atmosphericpressure, for example aerosol propellants such as halogenatedhydrocarbons, or else butane, propane, nitrogen and carbon dioxide.Suitable solid carriers are: for example ground natural minerals such askaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite ordiatomaceous earth, and ground synthetic minerals such as finely dividedsilica, alumina and silicates. Suitable solid carriers for granules are:for example crushed and fractionated natural rocks such as calcite,marble, pumice, sepiolite and dolomite, or else synthetic granules ofinorganic and organic meals, and granules of organic material such assawdust, coconut shells, maize cobs and tobacco stalks. Suitableemulsifiers and/or foam formers are: for example nonionic and anionicemulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylenefatty alcohol ethers, for example alkylaryl polyglycol ethers,alkylsulphonates, alkyl sulphates, arylsulphonates, or else proteinhydrolysates. Suitable dispersants are: for example lignosulphite wasteliquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, or else naturalphospholipids such as cephalins and lecithins and syntheticphospholipids can be used in the formulations. Other possible additivesare mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs suchas alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs,and trace nutrients such as salts of iron, manganese, boron, copper,cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95% by weight ofactive compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be used as such orin their formulations, also in a mixture with known fungicides,bactericides, acaricides, nematicides or insecticides, to broaden, forexample, the activity spectrum or to prevent development of resistance.In many cases, synergistic effects are obtained, i.e. the activity ofthe mixture is greater than the activity of the individual components.

Examples of suitable mixing components are the following:

Fungicides:

aldimorph, ampropylfos, ampropylfos-potassium, andoprim, anilazine,azaconazole, azoxystrobin,

benalaxyl, benodanil, benomyl, benzamacril, benzamacril-isobutyl,bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S,bromuconazole, bupirimate, buthiobate,

calcium polysulphide, carpropamid, capsimycin, captafol, captan,carbendazim, carboxin, carvon, quinomethionate, chlobenthiazone,chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlozolinate,clozylacon, cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram,

debacarb, dichlorophen, diclobutrazole, diclofluanid, diclomezine,dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph,diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione,ditalimfos, dithianon, dodemorph, dodine, drazoxolon,

edifenphos, epoxiconazole, etaconazole, ethirimol, etridiazole,

famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram, fenhexamid,fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate,fentin hydroxide, ferbam, ferimzone, fluazinam, flumetover, fluoromide,fluquinconazole, flurprimidol, flusilazole, flusulfamide, flutolanil,flutriafol, folpet, fosetyl-aluminium, fosetyl-sodium, fthalide,fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole,furconazole-cis, furmecyclox, fluoxastrobin,

guazatine,

hexachlorobenzene, hexaconazole, hymexazole,

imazalil, imibenconazole, iminoctadine, iminoctadine albesilate,iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (IBP),iprodione, iprovalicarb, irumamycin, isoprothiolane, isovaledione,

kasugamycin, kresoxim-methyl, copper preparations, such as: copperhydroxide, copper naphthenate, copper oxychloride, copper sulphate,copper oxide, oxine-copper and Bordeaux mixture,

mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil,metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram,metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin,

nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,

ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim, oxyfenthiin,

paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen,picoxystrobin, pimaricin, piperalin, polyoxin, polyoxorim, probenazole,prochloraz, procymidone, propamocarb, propanosine-sodium, propiconazole,propineb, pyraclostrobin, pyrazophos, pyrifenox, pyrimethanil,pyroquilon, pyroxyfur, prothioconazole,

quinconazole, quintozene (PCNB), quinoxyfen,

sulphur and sulphur preparations, spiroxamine,

tebuconazole, tecloftalam, tecnazene, tetcyclacis, tetraconazole,thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram,tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol,triazbutil, triazoxide, trichlamide, tricyclazole, tridemorph,trifloxystrobin, triflumizole, triforine, triticonazole,

uniconazole,

validamycin A, vinclozolin, viniconazole,

zarilamide, zineb, ziram and also

Dagger G,

OK-8705,

OK-8801,

α-(1,1-dimethylethyl)-β-(2-phenoxyethyl)-1H-1,2,4-triazole-1-ethanol,

α-(2,4-dichlorophenyl)-β-fluoro-β-propyl-1H-1,2,4-triazole-1-ethanol,

α-(2,4-dichlorophenyl)-α-methoxy-α-methyl-1H-1,2,4-triazole-1-ethanol,

α-(5-methyl-1,3-dioxan-5-yl)-β-[[4-(trifluoromethyl)phenyl]methylene]-1H-1,2,4-triazole-1-ethanol,

(5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(1H-1,2,4-triazol-1-yl)-3-octanone,

(E)-α-(methoxyimino)-N-methyl-2-phenoxyphenylacetamide,

1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethanoneO-(phenylmethyl)oxime,

1-(2-methyl-1-naphthalenyl)-1H-pyrrole-2,5-dione,

1-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione,

1-[(diiodomethyl)sulphonyl]-4-methylbenzene,

1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]methyl]-1H-imidazole,

1-[[2-(4-chlorophenyl)-3-phenyloxiranyl]methyl]-1H-1,2,4-triazole,

1-[1-[2-[(2,4-dichlorophenyl)methoxy]phenyl]ethenyl]-1H-imidazole,

1-methyl-5-nonyl-2-(phenylmethyl)-3-pyrrolidinole,

2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoromethyl-1,3-thiazole-5-carboxanilide,

2,6-dichloro-5-(methylthio)-4-pyrimidinylthiocyanate,

2,6-dichloro-N-(4-trifluoromethylbenzyl)benzamide,

2,6-dichloro-N-[[4-(trifluoromethyl)phenyl]methyl]benzamide,

2-(2,3,3-triiodo-2-propenyl )-2H-tetrazole,

2-[(1-methylethyl)sulphonyl]-5-(trichloromethyl)-1,3,4-thiadiazole,

2-[[6-deoxy-4-O-(4-O-methyl-β-D-glycopyranosyl])-α-D-glucopyranosyl]amino]-4-methoxy-1H-pyrrolo[2,3-d]pyrimidine-5-carbonitrile,

2-aminobutane,

2-bromo-2-(bromomethyl)pentanedinitrile,

2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide,

2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)acetamide,

2-phenylphenol (OPP),

3,4-dichloro-1-[4-(difluoromethoxy)phenyl]-1H-pyrrole-2,5-dione,

3,5-dichloro-N-[cyano[(1-methyl-2-propynyl)oxy]methyl]benzamide,

3-(1,1-dimethylpropyl-1-oxo-1H-indene-2-carbonitrile,

3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]pyridine,

4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulphonamide,

4-methyltetrazolo[1,5-a]quinazolin-5(4H)-one,

8-hydroxyquinoline sulphate,

9H-xanthene-2-[(phenylamino)carbonyl]-9-carboxylic hydrazide,

bis-(1-methylethyl)-3-methyl-4-[(3-methylbenzoyl)oxy]-2,5-thiophenedicarboxylate,

cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)cycloheptanol,

cis-4-[3-[4-(1,1-dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethylmorpholine-hydrochloride,

ethyl[(4-chlorophenyl)azo]cyanoacetate,

potassium hydrogen carbonate,

methanetetrathiol sodium salt,

methyl1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate,

methyl N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate,

methyl N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate,

N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)acetamide,

N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)acetamide,

N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitrobenzenesulphonamide,

N-(4-cyclohexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidineamine,

N-(4-hexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidineamine,

N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)acetamide,

N-(6-methoxy-3-pyridinyl)cyclopropanecarboxamide,

N-[2,2,2-trichloro-1-[(chloroacetyl)amino]ethyl]benzamide,

N-[3-choro-4,5-bis-(2-propinyloxy)phenyl]-N′-methoxymethaneimidamide,

N-formyl-N-hydroxy-DL-alanine sodium salt,

O,O-diethyl[2-(dipropyamino)-2-oxoethyl]ethylphosphoramidothioate,

O-methyl S-phenyl phenylpropylphosphoramidothioate,

S-methyl 1,2,3-benzothiadiazole-7-carbothioate,

spiro[2H]-1-benzopyrane-2,1′(3′H)-isobenzofuran]-3′-one,

4-[3,4-dimethoxyphenyl)-3-(4-fluorophenyl)acryloyl]morpholine.

Bactericides:

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin,probenazole, streptomycin, tecloftalam, copper sulphate and other copperpreparations.

Insecticides/Acaricides/Nematicides:

abamectin, acephate, acetamiprid, acrinathrin, alanycarb, aldicarb,aldoxycarb, alpha-cypermethrin, alphamethrin, amitraz, avermectin, AZ60541, azadirachtin, azamethiphos, azinphos A, azinphos M, azocyclotin,

Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillusthuringiensis, baculoviruses, Beauveria bassiana, Beauveria tenella,bendiocarb, benfuracarb, bensultap, benzoximate, betacyfluthrin,bifenazate, bifenthrin, bioethanomethrin, biopermethrin, bistrifluron,BPMC, bromophos A, bufencarb, buprofezin, butathiofos, butocarboxim,butylpyridaben,

cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap,chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos,chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M,chlovaporthrin, chromafenozide, cis-resmethrin, cispermethrin,clocythrin, cloethocarb, clofentezine, clothianidine, cyanophos,cycloprene, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin,cypermethrin, cyromazine,

deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron,diazinon, dichlorvos, dicofol, diflubenzuron, dimethoate,dimethylvinphos, diofenolan, disulfoton, docusat-sodium, dofenapyn,

eflusilanate, emamectin, empenthrin, endosulfan, Entomopfthora spp.,esfenvalerate, ethiofencarb, ethion, ethoprophos, etofenprox, etoxazole,etrimfos,

fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenothiocarb,fenoxacrim, fenoxycarb, fenpropathrin, fenpyrad, fenpyrithrin,fenpyroximate, fenvalerate, fipronil, fluazinam, fluazuron,flubrocythrinate, flucycloxuron, flucythrinate, flufenoxuron,flumethrin, flutenzine, fluvalinate, fonophos, fosmethilan, fosthiazate,fubfenprox, furathiocarb,

granulosis viruses,

halofenozide, HCH, heptenophos, hexaflumuron, hexythiazox, hydroprene,

imidacloprid, indoxacarb, isazofos, isofenphos, isoxathion, ivermectin,

nuclear polyhedrosis viruses,

lambda-cyhalothrin, lufenuron,

malathion, mecarbam, metaldehyde, methamidophos, Metharhiziumanisopliae, Metharhizium flavoviride, methidathion, methiocarb,methoprene, methomyl, methoxyfenozide, metolcarb, metoxadiazone,mevinphos, milbemectin, milbemycin, monocrotophos,

naled, nitenpyram, nithiazine, novaluron,

omethoate, oxamyl, oxydemethon M,

Paecilomyces fumosoroseus, parathion A, parathion M, permethrin,phenthoate, phorat, phosalone, phosmet, phosphamidon, phoxim,pirimicarb, pirimiphos A, pirimiphos M, profenofos, promecarb,propargite, propoxur, prothiofos, prothoat, pymetrozine, pyraclofos,pyresmethrin, pyrethrum, pyridaben, pyridathion, pyrimidifen,pyriproxyfen,

quinalphos,

ribavirin,

salithion, sebufos, silafluofen, spinosad, spirodiclofen, sulfotep,sulprofos,

tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos,teflubenzuron, tefluthrin, temephos, temivinphos, terbufos,tetrachlorvinphos, tetradifon theta-cypermethrin, thiacloprid,thiamethoxam, thiapronil, thiatriphos, thiocyclam hydrogen oxalate,thiodicarb, thiofanox, thuringiensin, tralocythrin, tralomethrin,triarathene, triazamate, triazophos, triazuron, trichlophenidine,trichlorfon, triflumuron, trimethacarb,

vamidothion, vaniliprole, Verticillium lecanii,

YI 5302

zeta-cypermethrin, zolaprofos

(1R-cis)-[5-(phenylmethyl)-3-furanyl]methyl3-[(dihydro-2-oxo-3(2H)-furanylidene)methyl]-2,2-dimethylcyclopropanecarboxylate,

(3-phenoxyphenyl)methyl 2,2,3,3-tetramethylcyclopropanecarboxylate,

1-[(2-chloro-5-thiazolyl)methyl]tetrahydro-3,5-dimethyl-N-nitro-1,3,5-triazine-2(1H)-imine,

2-(2-chloro-6-fluorophenyl)-4-[4-(1,1-dimethylethyl)phenyl]-4,5-dihydrooxazole,

2-(acetyloxy)-3-dodecyl-1,4-naphthalenedione,

2-chloro-N-[[[4-(1-phenylethoxy)phenyl]amino]carbonyl]benzamide,

2-chloro-N-[[[4-(2,2-dichloro-1,1-difluoroethoxy)phenyl]amino]carbonyl]benz-amide,

3-methylphenyl propylcarbamate,

4-[4-(4-ethoxyphenyl)-4-methylpentyl]-1-fluoro-2-phenoxybenzene,

4-chloro-2-(1,1-dimethylethyl)-5-[[2-(2,6-dimethyl-4-phenoxyphenoxy)ethyl]thio]-3(2H)-pyridazinone,

4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy]-3(2H)-pyridazinone,

4-chloro-5-[(6-chloro-3-pyridinyl)methoxy]-2-(3,4-dichlorophenyl)-3(2H)-pyridazinone,

Bacillus thuringiensis strain EG-2348,

[2-benzoyl-1-(1,1-dimethylethyl)-hydrazidobenzoic acid,

2,2-dimethyl-3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro[4.5]dec-3-en-4-ylbutanoate,

[3-[(6-chloro-3-pyridinyl)methyl]-2-thiazolidinylidene]cyanamide,

dihydro-2-(nitromethylene)-2H-1,3-thiazine-3(4H)carboxaldehyde,

ethyl[2-[[1,6-dihydro-6-oxo-1-(phenylmethyl)-4-pyridazinyl]oxy]ethyl]carbamate,

N-(3,4,4-trifluoro-1-oxo-3-butenyl)glycine,

N-(4-chlorophenyl)-3-[4-(difluoromethoxy)phenyl]-4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide,

N-[(2-chloro-5-thiazolyl)methyl]-N′-methyl-N″-nitroguanidine,

N-methyl-N′-(1-methyl-2-propenyl)-1,2-hydrazinedicarbothioamide,

N-methyl-N′-2-propenyl-1,2-hydrazinedicarbothioamide,

O,O-diethyl[2-(dipropylamino)-2-oxoethyl]ethylphosphoramidothioate,

N-cyanomethyl-4-trifluoromethylnicotinamide,

3,5-dichloro-1-(3,3-dichloro-2-propenyloxy)-4-[3-(5-trifluoromethylpyridin-2-yloxy)propoxy]benzene.

A mixture with other known active compounds, such as herbicides, or withfertilizers and growth regulators, is also possible.

In addition, the compounds of the formula (I) according to the inventionalso have very good antimycotic activity. They have a very broadantimycotic activity spectrum in particular against dermatophytes andyeasts, moulds and diphasic fungi (for example against Candida species,such as Candida albicans, Candida glabrata), and Epidermophytonfloccosum, Aspergillus species, such as Aspergillus niger andAspergillus fumigatus, Trichophyton species, such as Trichophytonmentagrophytes, Microsporon species such as Microsporon canis andaudouinii. The list of these fungi by no means limits the mycoticspectrum covered, but is only for illustration.

The active compounds can be used as such, in the form of theirformulations or the use forms prepared therefrom, such as ready-to-usesolutions, suspensions, wettable powders, pastes, soluble powders, dustsand granules. Application is carried out in a customary manner, forexample by watering, spraying, atomizing, broadcasting, dusting,foaming, spreading, etc. It is furthermore possible to apply the activecompounds by the ultra-low-volume method, or to inject the activecompound preparation or the active compound itself into the soil. It isalso possible to treat the seeds of the plants.

When using the active compounds according to the invention asfungicides, the application rates can be varied within a relatively widerange, depending on the kind of application. For the treatment of partsof plants, the active compound application rates are generally between0.1 and 10,000 g/ha, preferably between 10 and 1000 g/ha. For seeddressing, the active compound application rates are generally between0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 gper kilogram of seed. For the treatment of the soil, the active compoundapplication rates are generally between 0.1 and 10,000 g/ha, preferablybetween 1 and 5000 g/ha.

When used as insecticides, the active compounds according to theinvention can furthermore be present in their commercially availableformulations and in the use forms, prepared from these formulations, asa mixture with synergistic agents. Synergistic agents are compoundswhich increase the action of the active compounds, without it beingnecessary for the synergistic agent added to be active itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms.

When used against hygiene pests and pests of stored products, the activecompound is distinguished by an excellent residual action on wood andclay as well as by a good stability to alkali on limed substrates.

As already mentioned above, it is possible to treat all plants and theirparts according to the invention. In a preferred embodiment, wild plantspecies and plant cultivars, or those obtained by conventionalbiological breeding, such as crossing or protoplast fusion, and partsthereof, are treated. In a further preferred embodiment, transgenicplants and plant cultivars obtained by genetic engineering, ifappropriate in combination with conventional methods (GeneticallyModified Organisms), and parts thereof are treated. The term “parts” or“parts of plants” or “plant parts” has been explained above.

Particularly preferably, plants of the plant cultivars which are in eachcase commercially available or in use are treated according to theinvention. Plant cultivars are understood as meaning plants with novelproperties (“traits”) which are grown by conventional cultivation, bymutagenesis or by recombinant DNA techniques. These may be cultivars,biotypes or genotypes.

Depending on the plant species or plant cultivars, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, reduced application ratesand/or a widening of the activity spectrum and/or an increase in theactivity of the substances and compositions to be used according to theinvention, better plant growth, increased tolerance to high or lowtemperatures, increased tolerance to drought or to water or soil saltcontent, increased flowering performance, easier harvesting, acceleratedmaturation, higher harvest yields, better quality and/or a highernutritional value of the harvested products, better storage stabilityand/or processability of the harvested products are possible whichexceed the effects which are actually to be expected.

The transgenic plants or plant cultivars (i.e. those obtained by geneticengineering) which are preferably to be treated according to theinvention include all plants which, in the genetic modification,received genetic material which imparted particularly advantageoususeful properties (“traits”) to these plants. Examples of suchproperties are better plant growth, increased tolerance to high or lowtemperatures, increased tolerance to drought or to water or soil saltcontent, increased flowering performance, easier harvesting, acceleratedmaturation, higher harvest yields, better quality and/or a highernutritional value of the harvested products, better storage stabilityand/or processability of the harvested products. Further andparticularly emphasized examples of such properties are a better defenceof the plants against animal and microbial pests, such as againstinsects, mites, phytopathogenic fungi, bacteria and/or viruses, and alsoincreased tolerance of the plants to certain herbicidally activecompounds. Examples of transgenic plants which may be mentioned are theimportant crop plants, such as cereals (wheat, rice), maize, soya beans,potatoes, cotton, oilseed rape and also fruit plants (with the fruitsapples, pears, citrus fruits and grapes), and particular emphasis isgiven to maize, soya beans, potatoes, cotton and oilseed rape. Traitsthat are emphasized are in particular increased defence of the plantsagainst insects by toxins formed in the plants, in particular thoseformed in the plants by the genetic material from Bacillus thuringiensis(for example by the genes CryIA(a), CryIA(b), CryIA(c), CrylIA, CryIIIA,CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CryIF and also combinations thereof)(hereinbelow referred to as “Bt plants”). Traits which are alsoparticularly emphasized are the increased resistance of plants to fungi,bacteria and viruses by systemic acquired resistance (SAR), systemin,phytoalexins, elicitors and resistance genes and correspondinglyexpressed proteins and toxins. Traits that are furthermore particularlyemphasized are the increased tolerance of the plants to certainherbicidally active compounds, for example imidazolinones,sulphonylureas, glyphosate or phosphinotricin (for example the “PAT”gene). The genes which impart the desired traits in question can also bepresent in combination with one another in the transgenic plants.Examples of “Bt plants” which may be mentioned are maize varieties,cotton varieties, soya bean varieties and potato varieties which aresold under the trade names YIELD GARD® (for example maize, cotton, soyabeans), KnockOut® (for example maize), StarLink® (for example maize),Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato). Examples ofherbicide-tolerant plants which may be mentioned are maize varieties,cotton varieties and soya bean varieties which are sold under the tradenames Roundup Ready® (tolerance to glyphosate, for example maize,cotton, soya bean), Liberty Link® (tolerance to phosphinotricin, forexample oilseed rape), IMI® (tolerance to imidazolinones) and STS®(tolerance to sulphonylureas, for example maize). Herbicide-resistantplants (plants bred in a conventional manner for herbicide tolerance)which may be mentioned include the varieties sold under the nameClearfield® (for example maize). Of course, these statements also applyto plant cultivars having these genetic traits or genetic traits stillto be developed, which cultivars will be developed and/or marketed inthe future.

The plants listed can be treated according to the invention in aparticularly advantageous manner with the compounds of the formula I orthe active compound mixtures according to the invention. The preferredranges stated above for the active compounds or mixtures also apply tothe treatment of these plants. Particular emphasis is given to thetreatment of plants with the compounds or mixtures specificallymentioned in the present text.

The invention is illustrated by the following examples.

PREPARATION EXAMPLES Examples 1 and 2

2.5 g (7.3 mmol) of3-cyano-5,7-dichloro-6-(2-chloro-4-fluorophenyl)pyrazolo[1,5-a]pyrimidineand 0.425 g (7.3 mmol) of potassium fluoride in 7.8 g of acetonitrileare stirred at 60° C. for 3 hours. 3.31 g (29.3 mmol) of(S)-1,1,1-trifluoroprop-2-ylamine are then added, and the mixture isstirred at 80° C. for another 15 hours. The solvent is distilled offunder reduced pressure and the residue is treated with dichloromethaneand 1 N aqueous hydrochloric acid. The organic phase is separated offand dried over sodium sulphate, and the solvent is distilled off underreduced pressure. The residue is chromatographed on silica gel using amixture of 4 parts of cyclohexane and 1 part of ethyl acetate. Twodifferent product fractions (fraction 1 and fraction 2) are isolated.

Fraction 1 (1.2 g) is chromatographed again on silica gel using amixture of 9 parts of n-hexane and 1 part of acetone. This gives 0.8 g(21% of theory) of3-cyano-5-chloro-6-(2-chloro-4-fluorophenyl)-7-(S)-1′,1′,1′-trifluoroprop-2-ylaminopyrazolo[1,5-a]pyrimidineas atropisomer A (Example 1) (purity: 80.4%)

HPLC: log P=3.88 (isomer AS)

¹H-NMR (DMSO-d6, tetramethylsilane): δ=1.37, 1.38 (3H); 4.88, 4.90 (1H);7.43-7.59 (1H); 7.60-7.66 (1H); 7.72-7.78 (1H); 8.06, 8.08 (1H, NH);8.83 (1H) ppm.

Fraction 2, isolated last, contains 0.9 g (29.3% of theory) of3-cyano-5-chloro-6-(2-chloro-4-fluorophenyl)-7-(S)-1′,1′,1′-trifluoroprop-2-ylaminopyrazolo[1,5-a]pyrimidineas atropisomer B (Example 2) (purity: 99.3%)

HPLC: log P=3.91 (isomer BS)

¹H-NMR (DMSO-d6, tetramethylsilane): δ=1.29, 1.31 (3H); 4.61, 4.63 (1H);7.42-7.47 (1H); 7.58-7.61 (1H); 7.73-7.76 (1H); 8.10, 8.12 (1H, NH);8.84 (1H) ppm.

Example 3

0.165 g (9.75 g, 237.5 mmol) of potassium fluoride and 0.481 g (4.26mmol) of (S)-1,1,1-trifluoroprop-2-ylamine are added to a solution of0.5 g (1.4 mmol) of3,5,7-trichloro-6-(2,4,6-trifluorophenyl)pyrazolo[1,5-a]pyrimidine in12.5 ml of acetonitrile, and the mixture is stirred at 80° C. for 16hours. After cooling, 1N of hydrochloric acid and dichlormethane areadded. The reaction mixture is filtered and the filtrate isconcentrated. The residue is chromatographed on a silica gel cartridgeusing methyl t-butyl ether/petroleum ether (1:100). This gives 0.25 g(40% of theory) ofN-[3,5-dichloro-6-(2,4,6-trifluorophenyl)pyrazolo[1,5-a]pyrimidin-7-yl]-N-[(1S)-2,2,2-trifluoro-1-methylethyl]amine.

HPLC; log P=4.43

Example 4

0.1 g (0.33 mmol) of7-chloro-6-(2-chloro-6-fluorophenyl)pyrazolo[1,5-a]pyrimidine-3-carbonitrileand 0.028 g (0.33 mmol) of 1,2-dimethylpropylamine are dissolved in 5 mlof dichloromethane. 0.05 ml of triethylamine is added, and the reactionmixture is stirred at room temperature for 16 hours. The reactionmixture is stirred with 1N hydrochloric acid and then filtered, and thefiltrate is concentrated under reduced pressure. The residue ischromatographed on a silica gel cartridge using methyl t-butylether/petroleum ether (1:9). This gives 0.1 g (89% of theory) of6-(2-chloro-6-fluorophenyl)-7-[(1,2-dimethylpropyl)amino)pyrazolo[1,5-a]pyrimidine-3-carbonitrile.

HPLC; log P=3.78

Example 5

0.1 g (0.316 mmol) of7-chloro-6-(2-chloro-6-fluorophenyl)pyrazolo[1,5-a]pyrimidine-3-carbonitrileand 0.028 g (0.316 mmol) of 1,2-dimethylpropylamine are dissolved in 4ml of acetonitrile. 0.044 g (0.316 mmol) of potassium carbonate isadded, and the reaction mixture is stirred at 60° C. for 16 hours. 20 mlof ether and 10 ml of 1N hydrochloric acid are added to the reactionmixture. The organic phase is separated off, dried over sodium sulphateand concentrated under reduced pressure.

The residue is chromatographed on a silica gel cartridge using methylt-butyl ether/petroleum ether (1:30). This gives 0.08 g (67% of theory)ofN-[3-chloro-6-(2-chloro-4-fluorophenyl)pyrazolo[1,5-a]pyrimidin-7-yl]-N-(1,2-dimethylpropyl)amine.

HPLC; log P=4.53

The compounds of the formula

listed in Table 1 below are also prepared by the methods describedabove. TABLE 1 Ex. No. R¹ R² R³ X¹ X² Isomer** logP (° C.) m.p.: 6—CH₂—C(CH₃)═CH₂ —C₂H₅ 2,4,6-trifluorophenyl —Cl —CN 4.6 72,2,2-trifluoro-1-methylethyl —H 2,4,6-trifluorophenyl —Cl —CN S 3.69 8—CH₂—C(CH₃)═CH₂ —C₂H₅ 2-fluorophenyl —Cl —CN 4.38 9 2-methoxyethyl —C₂H₅2-fluorophenyl —Cl —CN 3.52 10 cyclopentyl —H 2-fluorophenyl —Cl —CN3.89 Fp.: 11 cyclopropylmethyl —H 2-fluorophenyl —Cl —CN 3.47 122,2,2-trifluoro-1-methylethyl —H 2-chloro-6-fluorophenyl —Cl —CN S 3.7313 —CH₂—C(CH₃)═CH₂ —C₂H₅ 2-chloro-6-fluorophenyl —Cl —CN 4.68 14—CH₂—CH₂—O—CH₂—CH₂— * 2-chloro-6-fluorophenyl —Cl —CN 3.26 15 n-butyl—C₂H₅ 2-chloro-6-fluorophenyl —Cl —CN 4.92 16 i-butyl —H2-chloro-6-fluorophenyl —Cl —CN 3.94 17 —CH₂—C(CH₃)₃ —H2-chloro-6-fluorophenyl —Cl —CN 4.41 18 —CH₂—C(CH₃)═CH₂ —H2-chloro-6-fluorophenyl —Cl —CN 3.65 19 —CH₂—CH₂—CH₂—CH₂— *2-chloro-6-fluorophenyl —Cl —CN 3.82 20 —C₂H₅ —C₂H₅2-chloro-6-fluorophenyl —Cl —CN 4.13 21 —CH₂—CH—CH₂—CH₂—CH₂— *2-chloro-6-fluorophenyl —Cl —CN 4.32 22 cyclopentyl —H2-chloro-6-fluorophenyl —Cl —CN 4.13 23 i-propyl —H2-chloro-6-fluorophenyl —Cl —CN 3.65 24 2-methoxyethyl —H2-chloro-6-fluorophenyl —Cl —CN 3.22 25 cyclopropyl —H2-chloro-6-fluorophenyl —Cl —CN 3.37 26 —CH₂—CH₂—S—CH₂—CH₂— *2-chloro-6-fluorophenyl —Cl —CN 3.9 27 —CH₂—CH₂—CH(CF₃)—CH₂—CH₂— *2-chloro-6-fluorophenyl —Cl —CN 4.37 28 —CH₂—CH₂—CH(CH₃)—CH₂—CH₂— *2-chloro-6-fluorophenyl —Cl —CN 4.77 29 cyclopropylmethyl —H2-chloro-6-fluorophenyl —Cl —CN 3.74 30 2-butyl —H2-chloro-6-fluorophenyl —Cl —CN 3.94 31 —CH₂—CH₂—CH═CH—CH₂— *2-chloro-6-fluorophenyl —Cl —CN 4.08 32 —CH₂—CH₂—CH₂—CH(CH₃)—CH₂— *2-chloro-6-fluorophenyl —Cl —CN 4.77 33 —CH₂—CH₂—CH═C(CH₃)—CH₂— *2-chloro-6-fluorophenyl —Cl —CN 4.51 34 —CH₂—CH₂—CHF—CH₂—CH₂— *2-chloro-6-fluorophenyl —Cl —CN 3.82 35 allyl —C₂H₅2-chloro-6-fluorophenyl —Cl —CN 4.32 36 (2-furyl)methyl —C₂H₅2-chloro-6-fluorophenyl —Cl —CN 4.32 37 (2-tetrahydrofuryl)methyl —C₂H₅2-chloro-6-fluorophenyl —Cl —CN 4.08 38 2-methoxyethyl —C₂H₅2-chloro-6-fluorophenyl —Cl —CN 3.86 39 —CH₂—COOC₂H₅ —C₂H₅2-chloro-6-fluorophenyl —Cl —CN 3.86 40 propargyl —CH₃2-chloro-6-fluorophenyl —Cl —CN 3.53 41 —CH₂—COOC₂H₅ —CH₃2-chloro-6-fluorophenyl —Cl —CN 3.57 42 1,3-dioxolan-2-ylmethyl —CH₃2-chloro-6-fiuorophenyl —Cl —CN 3.49 43 allyl —CH₃2-chloro-6-fluorophenyl —Cl —CN 4.03 44 (2-furyl)methyl —CH₃2-chloro-6-fluorophenyl —Cl —CN 3.99 45 —CH₂—C(CH₃)═CH₂ —CH₃2-chloro-6-fluorophenyl —Cl —CN 4.37 46 i-butyl —CH₃2-chloro-6-fluorophenyl —Cl —CN 4.51 47 (2-tetrahydrofuryl)methyln-propyl 2-chloro-6-fluorophenyl —Cl —CN 4.51 48 i-butyl —H2,4,6-trifluorophenyl —Cl —CN 3.85 49 —CH₂—C(CH₃)₃ —H2,4,6-trifluorophenyl —Cl —CN 4.26 50 2-butyl —H 2,4,6-trifluorophenyl—Cl —CN 3.89 51 cyclopentyl —H 2,4,6-trifluorophenyl —Cl —CN 4.01 52i-propyl —H 2,4,6-trifluorophenyl —Cl —CN 3.54 53 cyclopropyl —H2,4,6-trifluorophenvl —Cl —CN 3.25 54 cyclopropylmethyl —H2,4,6-trifluorophenyl —Cl —CN 3.63 55 —CH₂—C(CH₃)═CH₂ —H2,4,6-trifluorophenyl —Cl —CN 3.54 56 1,3-dioxolan-2-ylmethyl —CH₃2,4,6-trifluorophenyl —Cl —CN 3.33 57 2-methoxyethyl —C₂H₅2,4,6-trifluorophenyl —Cl —CN 3.74 58 —CH₂—CH₂—CH₂—CH₂—CH(CH₃)— *2,4,6-trifluorophenyl —Cl —CN 4.5 59 2-butyl —H 2-fluorophenyl —Cl —CN3.7 60 —CH₂—CH₂—CF₃ —H 2-fluorophenyl —Cl —CN 3.34 61 n-propyl —H2-fluorophenyl —Cl —CN 3.38 62 i-propyl —H 2-fluorophenyl —Cl —CN 3.3663 cyclohexyl —H 2-fluorophenyl —Cl —CN 4.2 64 1-cyclohexylethyl —H2-fluorophenyl —Cl —CN 4.91 65 2-methoxyethyl —H 2-fluorophenyl —Cl —CN2.89 66 cyclopropyl —H 2-fluorophenyl —Cl —CN 3.11 67 —CH₂—CF₃ —H2-fluorophenyl —Cl —CN 3.15 68 —CH₂—C(CH₃)═CH₂ —H 2-fluorophenyl —Cl —CN3.39 69 3-trifluoromethylcyclohexyl —H 2-fluorophenyl —Cl —CN 4.15 702-trifluoromethylcyclohexyl —H 2-fluorophenyl —Cl —CN 4.26 71 3,5- —H2-fluorophenyl —Cl —CN 4.26 bistrifluoromethylcyclohexyl 72 —C₂H₅ —C₂H₅2-fluorophenyl —Cl —CN 3.8 73 —CH₂—CH₂—O—CH₂—CH₂— * 2-fluorophenyl —Cl—CN 2.88 74 2,2,2-trifluoro-1- —H 2-fluorophenyl —Cl —CN S 3.49methylethyl 75 —CH(CH₃)—CH₂—CH(CH₃)₂ —H 2-fluorophenyl —Cl —CN 76i-butyl —H 2-chlorophenyl —Cl —CN 4 77 —CH₂—C(CH₃)₃ —H 2-chlorophenyl—Cl —CN 4.47 78 2-butyl —H 2-chlorophenyl —Cl —CN 3.98 79 cyclopentyl —H2-chlorophenyl —Cl —CN 4.19 80 i-propyl —H 2-chlorophenyl —Cl —CN 3.6481 cyclopropyl —H 2-chlorophenyl —Cl —CN 3.38 82 cyclopropylmethyl —H2-chlorophenyl —Cl —CN 3.74 83 —CH₂—C(CH₃)═CH₂ —H 2-chlorophenyl —Cl —CN3.68 84 —CH(CH₃)—CH₂—CH(CH₃)₂ —H 2-chlorophenyl —Cl —CN 4.7 851,3-dioxolan-2-ylmethyl —CH₃ 2-chlorophenyl —Cl —CN 3.42 86 allyl —CH₃2-chlorophenyl —Cl —CN 4.03 87 2-methoxyethyl —CH₃ 2-chlorophenyl —Cl—CN 3.5 88 —CH₂—C(CH₃)═CH₂ —CH₃ 2-chlorophenyl —Cl —CN 4.39 89—CH₂—C(CH₃)═CH₂ —C₂H₅ 2-chlorophenyl —Cl —CN 3.68 90 allyl —C₂H₅2-chlorophenyl —Cl —CN 4.32 91 —CH₂—CH₂—CH₂—CH(CH₃)— * 2-chlorophenyl—Cl —CN 4.18 92 —CH₂—CH₂—CH₂—CH₂— * 2-chlorophenyl —Cl —CN 3.82 93—CH₂—CH₂—CH═CH—CH₂— * 2-chlorophenyl —Cl —CN 4.1 94—CH₂—CH₂—CH₂—CH₂—CH(CH₃)— * 2-chlorophenyl —Cl —CN 4.69 95—CH₂—CH₂—CH(CH₃)—CH₂—CH₂— * 2-chlorophenyl —Cl —CN 4.78 96—CH₂—CH₂—CH═C(CH₃)—CH₂— * 2-chlorophenyl —Cl —CN 4.52 97—CH₂—CH₂—CH(CF₃)—CH₂—CH₂— * 2-chlorophenyl —Cl —CN 4.35 98—CH₂—CH₂—CH₂—CH₂—CH₂— * 2-chlorophenyl —Cl —CN 4.36 99—CH₂—CH₂—O—CH₂—CH₂— * 2-chlorophenyl —Cl —CN 3.17 100—CH₂—CH₂—S—CH₂—CH₂— * 2-chlorophenyl —Cl —CN 3.88 101 —CH₂—CH₂—N(CH₃)₂—C₂H₅ 2-chloro-6-fluorophenyl —Cl —CN 1.9 102 —CH(CF₃)—CH₂—CH₂—CH₂— *2-chloro-6-fluorophenyl —Cl —CN 4.18 103 2,2,2-trifluoro-1-methylethyl—H 2-chlorophenyl —Cl —CN S 3.79 104 —CH₂—CH₂—CH₂—CH₂—CH₂— *2-fluorophenyl —Cl —CN 4.05 105 —CH₂—C(CH₃)═CH₂ —C₂H₅ 2,4-difluorophenyl—Cl —CN 4.47 95-98 106 —CH₂—C(CH₃)═CH₂ —C₂H₅ 2,4,6-trifluorophenyl —Cl—Cl 5.55 107 allyl —CH₃ 2,4,6-trifluorophenyl —Cl —CN 3.87 108 i-butyl—CH₃ 2,4,6-trifluorophenyl —Cl —CN 4.37 109 2-methoxyethyl —CH₃2,4,6-trifluorophenvl —Cl —CN 3.44 110 —CH₂—C(CH₃)═CH₂ —CH₃2,4,6-trifluorophenyl —Cl —CN 4.24 111 allyl —C₂H₅ 2,4,6-trifluorophenyl—Cl —CN 4.23 112 —CH₂—CH₂—CH₂—CH(CH₃)— * 2,4,6-trifluorophenyl —Cl —CN4.09 113 —CH(CF₃)—CH₂—CH₂—CH₂— * 2,4,6-trifluorophenyl —Cl —CN 4.12 114—CH₂—CH₂—CH₂—CH₂— * 2,4,6-trifluorophenyl —Cl —CN 3.71 115—CH₂—CH₂—CH═CH—CH₂— * 2,4,6-trifluorophenyl —Cl —CN 3.96 116—CH₂—CH₂—CH₂—CH(CH₃)—CH₂— * 2,4,6-trifluorophenyl —Cl —CN 4.6 117—CH₂—CH₂—CH(CH₃)—CH₂—CH₂— * 2,4,6-trifluorophenyl —Cl —CN 4.6 118—CH₂—CH₂—CH═C(CH₃)—CH₂— * 2,4,6-trifluorophenyl —Cl —CN 4.34 119—CH₂—CH₂—CHF—CH₂—CH₂— * 2,4,6-trifluorophenyl —Cl —CN 3.72 120—CH₂—CH₂—CH(CF₃)—CH₂—CH₂— * 2,4,6-trifluorophenyl —Cl —CN 4.26 121—CH₂—CH₂—CH₂—CH₂—CH₂— * 2,4,6-trifluorophenyl —Cl —CN 4.23 122—CH₂—CH₂—O—CH₂—CH₂— * 2,4,6-trifluorophenyl —Cl —CN 3.16 123—CH₂—CH₂—S—CH₂—CH₂— * 2,4,6-trifluorophenyl —Cl —CN 3.79 124 —CH₂—CF₃ —H2,4,6-trifluorophenyl —Cl —CN 3.37 125 —C₂H₅ —C₂H₅ 2,4-difluorophenyl—Cl —CN 126 2,2,2-trifluoro-1- —H 2,4-difluorophenyl —Cl —CN S 3.65123-25  methylethyl 127 —C₂H₅ —H 2-fluorophenyl —Cl —CN 3.06 128 —CH₂—CN—H 2-fluorophenyl —Cl —CN 2.45 129 —C(CH₃)₂—CF₃ —H 2-fluorophenyl —Cl—CN 4.01 130 4-trifluoromethylcyclohexyl —H 2-fluorophenyl —Cl —CN 4.2131 —CH₃ —CH₃ 2-fluorophenyl —Cl —CN 3.12 132 —CH₂—CH₂—CH₂—CH₂— *2-fluorophenyl —Cl —CN 3.56 133 —CH₂—CH₂—CH(CF₃)—CH₂—CH₂— *2-fluorophenyl —CI —CN 4.13 134 —CH₂—CH(CH₃)—O—CH(CH₃)— * 2-fluorophenyl—Cl —CN 3.67 CH₂— 135 —CH₂—CH₂—S—CH₂—CH₂— * 2-fluorophenyl —Cl —CN 3.63136 1-cyclopropylethyl —H 2,4,6-trifluorophenyl —Cl —Cl 4.66 137—CH₂—CF₃ —H 2-chlorophenyl —Cl —CN 3.43 138 i-butyl —CH₃ 2-chlorophenyl—Cl —CN 4.51 139 2-methoxyethyl n-propyl 2-chlorophenyl —Cl —CN 4.23 1402-methoxyethyl —C₂H₅ 2-chlorophenyl —Cl —CN 4.28 141—CH(CF₃)—CH₂—CH₂—CH₂— * 2-chlorophenyl —Cl —CN 4.19 142—CH₂—CH₂—CH₂—CH(CH₃)—CH₂— * 2-chlorophenyl —Cl —CN 4.82 143—CH₂—CH₂—CHF—CH₂—CH₂— * 2-chlorophenyl —Cl —CN 3.81 144 i-propyl —H2-chloro-4-fluorophenyl —Cl —CN 3.78 145 2,2,2-trifluoro-1-methylethyl—H 2-chloro-4-fluorophenyl —Cl —CN AS + BR 3.87 146 2,2,2-trifluoro-1-—H 2-chloro-4-fluorophenyl —Cl —CN AS + BR + 3.92 methylethyl BS + AR147 2,2,2-trifluoro-1-methylethyl —H 2-chloro-4-fluorophenyl —Cl —CNAS + BR 3.91 148 i-butyl —H 2,4-difluorophenyl —Cl —CN 3.87 149 n-butyl—H 2,4-difluorophenyl —Cl —CN 3.86 150 —CH₂—C(CH₃)₃ —H2,4-difluorophenyl —Cl —CN 4.23 151 2-butyl —H 2,4-difluorophenyl —Cl—CN 3.82 152 —CH₂—CH₂—CF₃ —H 2,4-difluorophenyl —Cl —CN 3.47 153n-propyl —H 2,4-difluorophenyl —Cl —CN 3.5 154 cyclopentyl —H2,4-difluorophenyl —Cl —CN 3.98 155 i-propyl —H 2,4-difluorophenyl —Cl—CN 3.5 156 cyclohexyl —H 2,4-difluorophenyl —Cl —CN 4.26 1571-cyclohexylethyl —H 2,4-difluorophenyl —Cl —CN 4.96 158 2-methoxyethyl—H 2,4-difluorophenyl —Cl —CN 3.06 159 cyclopropyl —H 2,4-difluorophenyl—Cl —CN 3.23 160 cyclopropylmethyl —H 2,4-difluorophenyl —Cl —CN 4.35161 —CH₂—C(CH₃)═CH₂ —H 2,4-difluorophenyl —Cl —CN 3.51 1623-trifluoromethylcyclohexyl —H 2,4-difluorophenyl —Cl —CN 4.2 1632-trifluoromethylcyclohexyl —H 2,4-difluorophenyl —Cl —CN 4.23 1644-trifluoromethylcyclohexyl —H 2,4-difluorophenyl —Cl —CN 4.21 165—CH(CH₃)—CH₂—CH(CH₃)₂ —H 2,4-difluorophenyl —Cl —CN 4.47 166—CH₂—CH₂—N(CH₃)₂ —CH₃ 2,4-difluorophenyl —Cl —CN 1.72 167 propargyl —CH₃2,4-difluorophenyl —Cl —CN 3.35 168 1,3-dioxolan-2-ylmethyl —CH₃2,4-difluorophenyl —Cl —CN 3.3 169 —CH₂—CH(OCH₃)₂ —CH₃2,4-difluorophenyl —Cl —CN 3.46 170 —CH₂—C(CH₃)═CH₂ —CH₃2,4-difluorophenyl —Cl —CN 4.16 171 n-butyl —CH₃ 2,4-difluorophenyl —Cl—CN 4.36 172 i-butyl —H 2,6-difluorophenyl —Cl —CN 3.73 173 —CH₂—C(CH₃)₃—H 2,6-difluorophenyl —Cl —CN 4.15 174 2-butyl —H 2,6-difluorophenyl —Cl—CN 3.71 175 —CH₂—CN —H 2,6-difluorophenyl —Cl —CN 2.49 176 cyclopentyl—H 2,6-difluorophenyl —Cl —CN 3.89 177 1-propyl —H 2,6-difluorophenyl—Cl —CN 3.39 178 2-methoxyethyl —H 2,6-difluorophenyl —Cl —CN 2.96 179cyclopropyl —H 2,6-difluorophenyl —Cl —CN 3.13 180 —CH₂—CF₃ —H2,6-difluorophenyl —Cl —CN 3.07 181 cyclopropylmethyl —H2,6-difluorophenyl —Cl —CN 3.5 182 —CH₂—C(CH₃)═CH₂ —H 2,6-difluorophenyl—Cl —CN 3.4 183 —CH(CH₃)—CH₂—CH(CH₃)₂ —H 2,6-difluorophenyl —Cl —CN 4.39184 propargyl —CH₃ 2,6-difluorophenyl —Cl —CN 3.27 185 —CH₂—COOC₂H₅ —CH₃2,6-difluorophenyl —Cl —CN 3.31 186 1,3-dioxolan-2-ylmethyl —CH₃2,6-difluorophenyl —Cl —CN 3.21 187 allyl —CH₃ 2,6-difluorophenyl —Cl—CN 3.77 188 i-butyl —CH₃ 2,6-difluorophenyl —Cl —CN 4.23 1892-methoxyethyl —CH₃ 2,6-difluorophenyl —Cl —CN 3.27 190 —CH₂—C(CH₃)═CH₂—CH₃ 2,6-difluorophenyl —Cl —CN 4.1 191 allyl —C₂H₅ 2,6-difluorophenyl—Cl —CN 4.07 192 (2-furyl)methyl —C₂H₅ 2,6-difluorophenyl —Cl —CN 4.04193 (2-tetrahydrofuryl)methyl —C₂H₅ 2,6-difluorophenyl —Cl —CN 3.84 1942-methoxyethyl —C₂H₅ 2,6-difluorophenyl —Cl —CN 3.59 195 —CH₂—COOC₂H₅—C₂H₅ 2,6-difluorophenyl —Cl —CN 3.61 196 n-butyl —C₂H₅2,6-difluorophenyl —Cl —CN 4.64 197 —C₂H₅ —C₂H₅ 2,6-difluorophenyl —Cl—CN 3.88 198 cyclopropylmethyl n-propyl 2,6-difluorophenyl —Cl —CN 4.65199 (2-tetrahydrofuryl)methyl n-propyl 2,6-difluorophenyl —Cl —CN 4.24200 2-methoxyethyl n-propyl 2,6-difluorophenyl —Cl —CN 3.96 201—CH₂—CH(OH)—CH₂CH₂— * 2,6-difluorophenyl —Cl —CN 2.47 202—CH₂—CH₂—CH₂—CH(CH₃)— * 2,6-difluorophenyl —Cl —CN 3.92 203—CH₂—CH₂—CH₂—CH₂— * 2,6-difluorophenyl —Cl —CN 3.55 204—CH₂—CH₂—CH₂—CH₂—CH(CH₃)— * 2,6-difluorophenyl —Cl —CN 4.4 205—CH₂—CH₂—CH₂—CH(CH₃)—CH₂— * 2,6-difluorophenyl —Cl —CN 4.46 206—CH₂—CH₂—CH(CH₃)—CH₂—CH₂— * 2,6-difluorophenyl —Cl —CN 4.46 207—CH₂—CH₂—CH═C(CH₃)—CH₂— * 2,6-difluorophenyl —Cl —CN 4.2 208—CH₂—CH₂—CH(CF₃)—CH₂—CH₂— * 2,6-difluorophenyl —Cl —CN 4.13 209—CH₂—CH₂—CH₂—CH₂—CH₂— * 2,6-difluorophenyl —Cl —CN 4.07 210—CH₂—CH₂—S—CH₂—CH₂— * 2,6-difluorophenyl —Cl —CN 3.65 2112-fluorocyclopropyl —H 2,4,6-trifluorophenyl —Cl —CN 3.06 212 i-butyl —H2,4,6-trifluorophenyl —Cl —Cl 4.7 213 allyl —C₂H₅ 2,4,6-trifluorophenyl—Cl —Cl 5.14 214 2-methoxyethyl —C₂H₅ 2,4,6-trifluorophenyl —Cl —Cl 4.61215 —CH₂—CH₂—CH₂—CH(CH₃)— * 2,4,6-trifluorophenyl —Cl —Cl 4.99 216—CH₂—CH₂—CH₂—CH₂— * 2,4,6-trifluorophenyl —Cl —Cl 4.56 217—CH₂—CH₂—CH(CH₃)—CH₂—CH₂— * 2,4,6-trifluorophenyl —Cl —Cl 5.59 218—CH₂—CH₂—CH═CH—CH₂— * 2,4,6-trifluorophenyl —Cl —Cl 4.84 219—CH₂—CH₂—CH₂—CH(CH₃)—CH₂— * 2,4,6-trifluorophenyl —Cl —Cl 5.59 220—CH₂—CH₂—CH₂—CH₂—CH₂— * 2,4,6-trifluorophenyl —Cl —Cl 5.14 221—CH₂—CH₂—O—CH₂—CH₂— * 2,4,6-trifluorophenyl —Cl —Cl 3.94 222—CH₂—C(CH₃)₃ —H 2,4,6-trifluorophenyl —Cl —Cl 5.19 223 cyclopropylmethyl—H 2,4,6-trifluorophenyl —Cl —Cl 4.41 224 —CH₂—CF₃ —H2,4,6-trifluorophenyl —Cl —Cl 4.08 225 —CH₂—C(CH₃)═CH₂ —H2,4,6-trifluorophenyl —Cl —Cl 4.32 226 allyl —CH₃ 2,4,6-trifluorophenyl—Cl —Cl 4.8 227 i-butyl —CH₃ 2,4,6-trifluorophenyl —Cl —Cl 5.31 2282-methoxyethyl —CH₃ 2,4,6-trifluorophenyl —Cl —Cl 4.23 229—CH₂—C(CH₃)═CH₂ —CH₃ 2,4,6-trifluorophenyl —Cl —Cl 5.17 230—CH₂—CH₂—CF₂—CH₂—CH₂— * 2,4,6-trifluorophenyl —Cl —CN 3.81 231—CH₂—CH₂—CF₂—CH₂—CH₂— * 2,4,6-trifluorophenyl —Cl —Cl 4.61 232 (2,2-—CH₃ 2,4,6-trifluorophenyl —Cl —CN 4.32 dichlorocyclopropyl)methyl 233(2,2- —CH₃ 2,4,6-trifluorophenyl —Cl —Cl 5.16 dichlorocyclopropyl)methyl234 2-fluorocyclopropyl —H 2,4,6-trifluorophenyl —Cl —Cl 3.72 235 —C₂H₅—H 2,4-difluorophenyl —Cl —CN 3.2 236 —CH₂—CF₃ —H 2,4-difluorophenyl —Cl—CN 3.34 237 3,5- —H 2,4-difluorophenyl —Cl —CN 4.41bistrifluoromethylcyclohexyl 238 —CH₂—COOC₂H₅ —CH₃ 2,4-difluorophenyl—Cl —CN 3.49 239 allyl —CH₃ 2,4-difluorophenyl —Cl —CN 3.87 240—CH₂—CH₂—CN —CH₃ 2,4-difluorophenyl —Cl —CN 2.98 241 —CH₂—CN —CH₃2,4-difluorophenyl —Cl —CN 2.95 242 —CH₂—COOCH₃ —CH₃ 2,4-difluorophenyl—Cl —CN 3.17 243 (2-furyl)methyl —CH₃ 2,4-difluorophenyl —Cl 13 CN 3.87244 i-butyl —CH₃ 2,4-difluorophenyl —Cl —CN 4.33 245 —CH₂—CH₂—O—CH═CH₂—CH₃ 2,4-difluorophenyl —Cl —CN 2.6 246 2-methoxyethyl —CH₃2,4-difluorophenyl —Cl —CN 3.41 247 —CH₃ —CH₃ 2,4-difluorophenyl —Cl —CN3.25 248 1,2-dimethylpropyl —H 2,4,6-trifluorophenyl —Cl —CN 4.17 2491,2-dimethylpropyl —H 2,4,6-trifluorophenyl —Cl —Cl 5.02 2501,2-dimethylpropyl —H 2,4,6-trifluorophenyl —Cl —Cl 5.02 2511,2-dimethylpropyl —H 2,4,6-trifluorophenyl —Cl —Cl 5.02 2521,2-dimethylpropyl —H 2,4,6-trifluorophenyl —Cl —CN 4.16 2531,2-dimethyipropyl —H 2,4,6-trifluorophenyl —Cl —CN 4.16 254—O—CH₂—CH₂—CH₂—CH₂— * 2,4-difluorophenyl —Cl —CN 3.71 255—O—CH₂—CH₂—CH₂—CH₂— * 2-chloro-4-fluorophenyl —Cl —CN 4.02 256—O—CH₂—CH₂—CH₂—CH₂— * 2-chloro-6-fluorophenyl —Cl —CN 3.85 2571,2-dimethylpropyl —H 2-chloro-4-fluorophenyl —Cl —CN AS + BR 4.43 2581,2-dimethylpropyl —H 2-chloro-4-fluorophenyl —Cl —CN AR + BS 4.48 259i-butyl —H 2-chloro-4-fluorophenyl —Cl —CN 4.18 260 —CH₂—C(CH₃)₃ —H2-chloro-4-fluorophenyl —Cl —CN 4.61 261 2-butyl —H2-chloro-4-fluorophenyl —Cl —CN 4.18 262 cyclopentyl —H2-chloro-4-fluorophenyl —Cl —CN 4.32 263 2-methoxyethyl —H2-chloro-4-fluorophenyl —Cl —CN 3.33 264 cyclopropylmethyl —H2-chloro-4-fluorophenyl —Cl —CN 3.9 265 —CH₂—C(CH₃)═CH₂ —H2-chloro-4-fluorophenyl —Cl —CN 3.85 266 i-butyl —CH₃2-chloro-4-fluorophenyl —Cl —CN 4.67 267 2-methoxyethyl —CH₃2-chloro-4-fluorophenyl —Cl —CN 3.72 268 —CH₂—C(CH₃)═CH₂ —CH₃2-chloro-4-fluorophenyl —Cl —CN 4.5 269 —CH₂—C(CH₃)═CH₂ —C₂H₅2-chloro-4-fluorophenyl —Cl —CN 4.87 270 2-methoxyethyl —C₂H₅2-chloro-4-fluorophenyl —Cl —CN 3.99 271 —CH₂—CH₂—CH₂—CH(CH₃)— *2-chloro-4-fluorophenyl —Cl —CN 4.32 272 —CH₂—CH₂—CH₂—CH₂— *2-chloro-4-fluorophenyl —Cl —CN 3.99 273 —CH₂—CH₂—CH(CH₃)—CH₂—CH₂— *2-chloro-4-fluorophenyl —Cl —CN 4.92 274 —CH₂—CH₂—CH₂—CH₂—CH₂— *2-chloro-4-fluorophenyl —Cl —CN 4.51 275 —CH₂—CH₂—O—CH₂—CH₂— *2-chloro-4-fluorophenyl —Cl —CN 3.33 276 —CH₂—CF₃ —H2-chloro-4-fluorophenyl —Cl —CN 277 —CH(CF₃)—CH₂—CH₂—CH₂— *2-chloro-4-fluorophenyl —Cl —CN 278 1,2-dimethylpropyl —H2-chloro-6-fluorophenyl —H —Cl 4.43 279 —CH₂—C(CH₃)═CH₂ —C₂H₅2-chloro-4-fluorophenyl —H —Cl 5.14 280 —NH—CH₂—CH₂—CH₂—CH₂— *2-chloro-4-fluorophenyl —H —Cl 3.57 281 —NH—CH₂—CH₂—CH₂—CH₂— *2-chloro-6-fluorophenyl —H —Cl 3.6 282 —CH₂—CH₂—CH(COCH₃)—CH₂— *2,4-difluorophenyl —Cl —CN 3.31 CH₂— 283 —CH₂—CH═C(C₂H₅)—CH₂—CH₂— *2,4-difluorophenyl —Cl —CN 4.76 284 —CH₂—CH₂—CH═C(CH₃)—CH₂— *2,4-difluorophenyl —Cl —CN 4.33 285 —CH₂—CH₂—CH(COOCH₃)—CH₂— *2,4-difluorophenyl —Cl —CN 3.61 CH₂— 286 —CH₂—CH₂—CHBr—CH₂—CH₂— *2,4-difluorophenyl —Cl —CN 4.21 287 —CH(COOCH₃)—CH₂—CH₂—CH₂— *2,4-difluorophenyl —Cl —CN 3.85 CH₂— 288 —CH₂—CH₂—CHF—CH₂—CH₂— *2,4-difluorophenyl —Cl —CN 3.66 289

* 2,4-difluorophenyl —Cl —CN 4 290 —CH₂—CH₂—CH(CF₃)—CH₂—CH₂— *2,4-difluorophenyl —Cl —CN 4.2 291

* 2,4-difluorophenyl —Cl —CN 1.74 292 —CH₂—CH₂—CH(NH—COCH₃)— *2,4-difluorophenyl —Cl —CN 2.51 CH₂—CH₂— 293 —CH₂—CH₂—N(CH₃)—CH₂—CH₂— *2,4-difluorophenyl —Cl —CN 1.47 294 —CH₂—CH(CH₃)—O—CH(CH₃)— *2,4-difluorophenyl —Cl —CN 3.77 CH₂— 295 —CH₂—CH₂—CH₂—CH₂—CH₂— *2,4-difluorophenyl —Cl —CN 4.18 296 —CH₂—CH₂—S—CH₂—CH₂— *2,4-difluorophenyl —Cl —CN 3.73 297

* 2,4-difluorophenyl —Cl —CN 4.38 298 1,2-dimethylpropyl —H2,6-difluorophenyl —Cl —CN 4.02 299 —CH₂—CHF₂ —H 2-chloro-6-fluorophenyl—H —Cl 3.09 300 2-methoxyethyl n-propyl 2,4,6-trifluorophenyl —Cl —CN4.1 301 2,2,2-trifluoro-1-methylethyl —H 2,6-difluorophenyl —Cl —CN R3.47 302 1,2-dimethylpropyl —H 2-chloro-4-fluorophenyl —Cl —CN BR 4.44303 1,2-dimethylpropyl —H 2-chloro-4-fluorophenyl —Cl —CN AR 4.47 3041,2-dimethylpropyl —H 2-chloro-4-fluorophenyl —Cl —CN AR + BR 4.45 3051,2-dimethylpropyl —H 2-chloro-4-fluorophenyl —Cl —CN AS 4.46 3061,2-dimethylpropyl —H 2-chloro-4-fluorophenvl —Cl —CN BS 4.46 3071,2-dimethylpropyl —H 2-chloro-4-fluorophenyl —Cl —CN AS + BS 4.45 308—CH₂—CH₂—N(CH₃)₂ —C₂H₅ 2,4-difluorophenyl —Cl —CN 1.83 309 allyl —C₂H₅2,4-difluorophenyl —Cl —CN 4.18 310 (2-furyl)methyl —C₂H₅2,4-difluorophenyl —Cl —CN 4.18 311 (2-tetrahydrofuryl)methyl —C₂H₅2,4-difluorophenyl —Cl —CN 4.02 312 —CH₂—CH₂—CN —C₂H₅ 2,4-difluorophenyl—Cl —CN 3.24 313 2-methoxyethyl —C₂H₅ 2,4-difluorophenyl —Cl —CN 3.74314 —CH₂—COOC₂H₅ —C₂H₅ 2,4-difluorophenyl —Cl —CN 3.81 315 3-aminopropyln-propyl 2,4-difluorophenyl —Cl —CN 1.75 316 (2-tetrahydrofuryl)methyln-propyl 2,4-difluorophenyl —Cl —CN 4.45 317 2-thienylmethyl n-propyl2,4-difluorophenyl —Cl —CN 4.8 318 2-methoxyethyl n-propyl2,4-difluorophenyl —Cl —CN 4.13 319 —CH₂—CH₂—NH₂ -i-propyl2,4-difluorophenyl —Cl —CN 1.72 320 —CH₂—COOC₂H₅ cyclo-2,4-difluorophenyl —Cl —CN 3.99 propyl 321 —CH₂—CH(OH)—CH₂—CH₂— *2,4-difluorophenyl —Cl —CN 2.57 322 —CH₂—CH₂—CH₂—CH(CH₃)— *2,4-difluorophenyl —Cl —CN 4.05 323 —CH₂—CH₂—CH₂—CH₂— *2,4-difluorophenyl —Cl —CN 3.7 324 —CH₂—CH₂—CH(OH)—CH₂—CH₂— *2,4-difluorophenyl —Cl —CN 2.63 325

* 2,4-difluorophenyl —Cl —CN 3.51 326 —CH₂—CH(CH₃)—CH₂—CH(CH₃)— *2,4-difluorophenyl —Cl —CN 4.98 CH₂— 327 —CH₂—CH₂—CH₂—CH₂—CH(CH₃)— *2,4-difluorophenyl —Cl —CN 4.49 328 —CH₂—CH₂—CH₂—CH(CH₃)—CH₂— *2,4-difluorophenyl —Cl —CN 4.59 329 —CH₂—CH₂—CH(CH₃)—CH₂—CH₂— *2,4-difluorophenyl —Cl —CN 4.59 330 —CH₂—CH(OH)—CH₂—CH₂— *2,4-difluorophenyl —Cl —CN 2.83 CH₂— 331 —CH₂—CH₂—C(CH₃)₂—CH₂—CH₂— *2,4-difluorophenyl —Cl —CN 4.83 332 —CH₂—CH₂—S—CH₂—CH₂— *2,4,6-trifluorophenyl —Cl —Cl 4.64 333 1,2-dimethylpropyl —H2-chlorophenyl —Cl —Cl B 5.17 334 1,2-dimethylpropyl —H 2-chlorophenyl—Cl —Cl A 5.18 335 i-butyl —CH₃ 2-chlorophenyl —Cl —Cl 5.38 3361,2-dimethylpropyl —H 2-chloro-6-fluorophenyl —Cl —CN 4.25 3371,2-dimethylpropyl —H 2-chloro-6-fluorophenyl —Cl —CN 4.26 338—CH₂—CH₂—O—CH₂—CH₂— * 2-chlorophenyl —Cl —Cl 3.86 339—CH₂—CH₂—S—CH₂—CH₂ * 2-chlorophenyl —Cl —Cl 4.67 340—CH₂—CH₂—CF₂—CH₂—CH₂ * 2-chlorophenyl —Cl —Cl 4.67 3412,2,2-trifluoro-1- —H 2-chlorophenyl —Cl —Cl B 4.48 methylethyl 3422,2,2-trifluoro-1- —H 2-chlorophenyl —Cl —CI A 4.52 methylethyl 343—CH₂—CH₂—O—CH₂—CH₂— * 2-chloro-4-fluorophenyl —Cl —Cl 4.01 344—CH₂—CH₂—S—CH₂—CH₂ * 2-chloro-4-fluorophenyl —Cl —Cl 4.79 345—CH₂—CH₂—CF₂—CH₂—CH₂— * 2-chloro-4-fluorophenyl —Cl —Cl 4.79 346cyclopropylmethyl —H 2-chloro-4-fluorophenyl —Cl —Cl 4.57 347 —CH₂—CF₃—H 2-chloro-4-fluorophenyl —Cl —Cl 4.2 348 i-butyl —CH₃2-trifluoromethylphenyl —Cl —CN 4.48 349 —CH₂—C(CH₃)₃ —H2-trifluoromethylphenyl —Cl —CN 4.43 350 —CH₂—CH₂—CH(CH₃)—CH₂—CH₂ *2-trifluoromethylphenyl —Cl —CN 4.71 351 2,2,2-trifluoro-1- —H2-chloro-4-fluorophenyl —Cl —Cl B 4.63 methylethyl 3522,2,2-trifluoro-1- —H 2-chloro-4-fluorophenyl —Cl —Cl A 4.62 methylethyl353 1,2-dimethylpropyl —H 2-chloro-4-fluorophenyl —Cl —Cl B 5.26 3541,2-dimethylpropyl —H 2-chloro-4-fluorophenyl —Cl —Cl A 5.25 355—NH—CH₂—CH₂—CH₂—CH₂— * 2-chloro-6-fluorophenyl —Cl —CN 3.66 paste 356—NH₂ i-butyl 2-chloro-6-fluorophenyl —Cl —CN 3.9 oil 357 —CH₂—CF₃ —H2-trifluoromethylphenyl —Cl —CN 3.44 358 1,2-dimethylpropyl —H2-trifluoromethylphenyl —Cl —Cl A 5.04 359 1,2-dimethylpropyl —H2-trifluoromethylphenyl —Cl —Cl B 5.05 360 —CH₂—C(CH₃)₃ —H2-chlorophenyl —Cl —Cl 5.34 361 —CH₂—C(CH₃)₃ —H 2-chloro-4-fluorophenyl—Cl —Cl 5.4 362 —CH₂—CH₂—S—CH₂—CH₂— * 2-chloro-6-fluorophenyl —Cl —Cl4.79 363 —CH₂—CH₂—S—CH₂—CH₂— * 2-trifluoromethylphenyl —Cl —Cl 4.68 364—NH—CH₂—CH₂—CH₂—CH₂— * 2-trifluoromethylphenyl —Cl —Cl 4.41 365—CH₂—CH₂—O—CH₂—CH₂— * 2-trifluoromethylphenyl —Cl —Cl 3.9 3662,2,2-trifluoro-1- —H 2-trifluoromethylphenyl —Cl —Cl B 4.49 methylethyl367 2,2,2-trifluoro-1- —H 2-trifluoromethylphenyl —Cl —Cl A 4.46methylethyl 368 —NH—CH₂—CH₂—CH₂—CH₂— * 2-chloro-4-fluorophenyl —Cl —CN3.78 209-11  369 2,2,2-trifluoro-1- —H 2-trifluoromethylphenyl —Cl —CN A3.75 methylethyl 370 2,2,2-influoro-1- —H 2-trifluoromethylphenyl —Cl—CN B 3.79 methylethyl 371

* 2-trifluoromethylphenyl —Cl —Cl 4.17 372 —NH₂ i-butyl2-chloro-4-fluorophenyl —Cl —CN 4.09 paste 373—CH₂—CH₂—CH(CH₃)—CH₂—CH₂— * 2-chloro-6-fluorophenyl —Cl —Cl 5.77 374—NH—CH₂—CH₂—CH₂—CH₂ * 2-chloro-6-fluorophenyl —Cl —Cl 4.4 375 —NH₂i-butyl 2-chloro-6-fluorophenyl —H —Cl 4.11 oil 376 1,2-dimethylpropyl—H 2-trifluoromethylphenyl —Cl —CN 4.26 377 —NH₂ i-butyl2-trifluoromethylphenyl —Cl —CN 3.96 128-30  378 2,2,2-trifluoro-1- —H2-trifluoromethylphenyl —Cl —CN A 3.79 methylethyl 3792,2,2-trifluoro-1- —H 2-trifluoromethylphenyl —Cl —CN B 3.79 methylethyl380 2,2,2-trifluoro-1- —H 2,4,6-trifluorophenyl —Cl —Cl 4.42 methylethyl381 —CH₂—CH₂—CH₂—NH— * 2-chloro-6-fluorophenyl —Cl —CN 3.23 382—CH(CH₃)—C(CH₃)₃ —H 2-chloro-4-fluorophenyl —Cl —CN 4.78 180-5  383—CH(CH₃)—C(CH₃)₃ —H 2-chloro-6-flfuorphenyl —Cl —CN 4.6 384—CH(CH₃)—C(CH₃)₃ —H 2,4,6-trifluorophenyl —Cl —CN 4.51 385—CH₂—CH₂—O—CH₂—CH₂ * 2-chloro-5-nitrophenyl —Cl —NO₂ 2.91 3861,2,2-trimethylpropyl —H 2-chloro-6-fluorophenyl —Cl —CN 4.59 146-8  3871,2,2-trimethylpropyl —H 2-chloro-6-fluorophenyl —Cl —CN 4.66 145-8  388—CH(CH₃—C(CH₃)₃ —H 2-trifluoromethylphenyl —Cl —CN 4.57 389—CH(CH₃)—C(CH₃)₃ —H 2-chloro-4-fluorophenyl —Cl —Cl 5.63 3901,2,2-trimethylpropyl —H 2-chloro-4-fluorophenyl —Cl —CN 4.8 paste 3911,2,2-trimethylpropyl —H 2-chloro-4-fluorophenyl —Cl —CN 4.83 paste 392—CH₂—CH₂—O—CH₂—CH₂— * 2-chlorophenyl —Cl —Br 3.97 393 —CH(CH₃)—C(CH₃)₃—H 2-chloro-4-fluorophenyl —Cl —CSNH₂ 4.74 paste 3941,2,2-trimethylpropyl —H 2,4,6-trifluorophenyl —Cl —CN 4.55 395 i-butyl—H 2-chloro-4-methoxyphenyl —Cl —CN 4.01 396 —CH(CH₃)—C(CH₃)₃ —H2-chloro-4-methoxyphenyl —Cl —CN 4.67 397 —CH₂—C(CH₃)₃ —H2-chloro-4-methoxyphenyl —Cl —CN 4.45 398 1,2-dimethylpropyl —H2-chlorophenyl —Cl —Br 5.31 399 —CH₂—CH₂—O—CH₂—CH₂ * 2-chlorophenyl —ClI 4.13 400 1,2-dimethylpropyl —H 2-chlorophenyl —Cl I 5.43 401—CH(CH₃)—C(CH₃)₃ —H 2-chloro-4-fluorophenyl —Cl —CHO 4.43 402—CH(CH₃)—C(CH₃)₃ —H 2-chloro-4-fluorophenyl —Cl —CH═N—O— A + B 5.48paste CH₃ 403 —CH(CH₃)—C(CH₃)₃ —H 2-chloro-4-fluorophenyl —Cl —CH═N—O— A5.5 paste CH₃ 404 —CH(CH₃)—C(CH₃)₃ —H 2-chloro-4-fluorophenyl —Cl—CH═N—O— B 5.57 paste CH₃ 405 1,2-dimethylpropyl —H2-chloro-4-methoxyphenyl —Cl —CN 4.33 406 —CH₂—CH₂—CH₂—CH₂—CH(CH₃)— *2-chloro-4-methoxyphenyl —Cl —CN 4.65 407 1,2,2-trimethylpropyl —H2,4,6-trifluorophenyl —Cl cyclo- 5.88 propyl 408 —CH₂—CF₃ —H2-chloro-4-methylphenyl —Cl —CN 3.47 409 1,2-dimethylpropyl —H2-chlorophenyl —Cl —CHO 3.98 410 i-butyl —CH₃ 2-chloro-4-methoxypyhenyl—Cl —CN 4.5 411 —CH₂—CH₂—O—CH₂—CH₂— * 2-chloro-4-methoxypyhenyl —Cl —CN3.26 412 —CH₂—CH₂—CH₂—CH₂—CH(CH₃)— * 2-chloro-4-methoxypyhenyl —Cl —CN4.18 413 —CH₂—CH₂—CH(CN)—CH₂—CH₂ * 2-chloro-4-fluorophenyl —Cl —Cl 4.06414 1,2-dimethylpropyl —H 2,4,6-trifluorophenyl —Cl cyclo- 5.5 propyl415 —CH(CH₃—C(CH₃)₃ —H 2-chloro-6-fluorophenyl —Cl —CSNH₂ 4.52 4161,2-dimethylpropyl —H 2-chlorophenyl —Cl cyclo- 5.61 propyl 4171,2-dimethylpropyl —H 2,4,6-trifluorophenyl —Cl —Br 5.13 418—CH₂—CH₂—CH(CH₃)—CH₂—CH₂ * 2,4,6-trifluorophenyl —Cl —Br 5.65 419—CH₂—CH₂—O—CH₂—CH₂— * 2,4,6-trifluorophenyl —Cl —Br 3.97 4201,2,2-trimethylpropyl —H 2-chlorophenyl —Cl cyclo- 5.97 propyl 421

—H 2-chloro-4-fluorophenyl —Cl —CH₃ 4.79 422

—H 2-chloro-4-fluorophenyl —Cl —CHO 4.43 423

* 2-chlorophenyl —Cl —CHO 4.42 424

* 2-chloro-4-fluorophenyl —Cl —CHO 4.53 425

H 2-chlorophenyl —Cl —CHO 3.98 426 —CH₂—CH₂—O—CH₂—CH₂— *2,4,6-trifluorophenyl —Cl —CHO 2.78 427

* 2,4,6-trifluorophenyl —Cl —CHO 4.24 428

H 2-chloro-6-fluorophenyl —Cl —CHO 4.25 429 —NH—CH₂—CH₂—CH₂—CH₂ *2,4,6-trifluorophenyl —Cl —CHO 3.28 430

H 2,4,6-trifluorophenyl —Cl —CHO 3.52 431

* 2,4,6-trifluorophenyl —Cl —CHO 3.74 432 —CH₂—CH₂—S—CH₂—CH₂— *2,4,6-trifluorophenyl —Cl —CHO 3.45 433

H 2,4,6-trifluorophenyl —Cl —CHO 3.39 434 —CH₂—CH₂—O—CH₂—CH₂— *2-chloro-4-fluorophenyl —Cl —CHO 2.94 435 —CH₂—CH₂—S—CH₂—CH₂— *2-chlorophenyl —Cl —CHO 3.51 436

H 2,4,6-trifluorophenyl —Cl —CHO 3.16 437

* 2-chlorophenyl —Cl —CHO 3.80 438 —CH₂—CH₂—S—CH₂—CH₂— *2-chloro-4-fluor-phenyl —Cl —CHO 3.65 439

* 2-chloro-4-fluorophenyl —Cl —CHO 4.45 440

* 2-chloro-4-fluorophenyl —Cl —CHO 3.95# denotes the point of attachmentThe logP values were determined in accordance with EEC Directive 79/831Annex V. A8 by HPLC (gradient method, acetonitrile/0.1% aqueousphosphoric acid)*) means that R¹ and R² together with the nitrogen atom to which theyare attached form a heterocyclic ring.**) Some of the products were isolated as stereoisomers. “S” and “R”mean S configuration and R configuration, respectively, at the centre ofchirality; “AS” means an unambiguous but unknown configuration at thecentre of atropy and S configuration at the centre of chirality. BSmeans the respective other unambiguous but unknown configuration at thecentre of atropy and S configuration at the centre of chirality.# In turn, “AR” and “BR” mean the respective complementaryconfigurations at the centre of atrophy, combined with the Rconfiguration at the centre of chirality. Accordingly, in the case ofidentical substituents, “AR” and “BS”, and “AS” and “BR” are in eachcase pairs of enantiomers.

Preparation of the Compound of Example 401

Under an atmosphere of argon and stirring at −50° C., a 1-molar solutionof 649 mg (0.812 mmol) of diisobutylaluminium hydride in toluene isslowly added dropwise to a solution of 300 mg (0.738 mmol) of3-cyano-5-chloro-6-(2-chloro-4-fluorophenyl)-7-(1,2,2-trimethylpropylamino)pyrazolo[1,5a]pyrimidinein 13.2 g of dichloromethane. After the addition has ended, stirring at−50° C. is continued for another 30 minutes. The temperature of thereaction mixture is then allowed to increase to 0° C., saturated aqueousammonium chloride solution is added and the mixture is stirred at 0° C.for 2 hours. 1 N hydrochloric acid is added, the organic phase isseparated off and the aqueous phase is extracted three more times withdichloromethane. The combined organic phases are washed successivelywith saturated aqueous sodium bicarbonate solution and with saturatedaqueous sodium chloride solution, dried over sodium sulphate and thenconcentrated under reduced pressure. In this manner, 300 mg (99% oftheory) of3-formyl-5-chloro-6-(2-chloro-4-fluorophenyl)-7-(1,2,2-trimethylpropylamino)pyrazolo[1,5a]pyrimidine are obtained.

HPLC: log P=4.43.

Preparation of the Compound According to Example 402

At room temperature, 73 mg (0.880 mmol) of methoxyamine hydrochlorideand 1.0 g of the weak basic ion exchanger commercially available underthe name Amberlyst A-21 are added to a solution of 300 mg (0.733 mmol)of3-formyl-5-chloro-6-(2-chloro-4-fluorophenyl)-7-(1,2,2-trimethylpropylamino)pyrazlo[1,5a]pyrimidinein 20 ml of ethanol, and the mixture is shaken at room temperature for18 hours. The reaction mixture is then filtered, and the filtrate isconcentrated under reduced pressure. This gives 220 mg of3-methoximino-5-chloro-6-(2-chloro-4-fluorophenyl)-7-(1,2,2-trimethylpropylamino)pyrazolo[1,5a]pyrimidinein the form of a mixture of atropisomers.

HPLC: log P=5.48.

Preparation of Intermediates of the Formula (II) Example 441

Process (g):

48 g (0.184 mol) of dimethyl 2-chloro-4-fluorophenylmalonate are mixedwith 19.91 g (0.184 mol) of 4-cyano-5-aminopyrazole and with 37.55 g(0.203 mol) of tri-n-butylamine, and the mixture is stirred at 180° C.for 6 hours. The methanol formed during the reaction is distilled off.The reaction mixture is then cooled to room temperature. At 95° C. and 1mbar, volatile components are distilled off. The residue obtained is6-(2-chloro-4-fluorophenyl)-5,7-dihydroxypyrazolo[1,5-a]pyrimidine-3-carbonitrilein the form of a crude product which is used for further synthesiswithout additional purification.Process (e)

The6-(2-chloro-4-fluorophenyl)-5,7-dihydroxypyrazolo[1,5-a]pyrimidine-3-carbo-nitrileobtained above is, in crude form, dissolved in 367.3 g (2.395 mol) ofphosphorus oxychloride. At room temperature, 31.95 g (0.153 mol) ofphosphorus pentachloride is added a little at a time. The mixture isthen boiled under reflux for 12 hours. The volatile components aredistilled off under reduced pressure, dichloromethane is added to theresidue and the mixture is washed with water. The organic phase is driedover sodium sulphate and concentrated under reduced pressure. Theresidue is chromatographed on silica gel using 3 parts of cyclohexaneand 1 part of ethyl acetate as mobile phase. This gives 21 g of 95.7%pure3-cyano-5,7-dichloro-6-(2-chloro-4-fluorophenyl)pyrazolo[1,5-a]pyrimidine.

HPLC: log P=3.48

¹H-NMR (DMSO-d6, tetramethylsilane): δ=7.44-7.52 (1H); 7.62-7.66 (1H);7.71-7.77 (1H); 9.03 (1H) ppm.

Example 442

Process (e)

26 g (82.4 mmol) of3-chloro-6-(2,4,6-trifluorophenyl)pyrazolo[1,5-a]pyrimidine-5,7-diol and8.6 g (41.2 mmol) of phosphorus pentachloride are stirred in 126.3 g ofphosphorus oxychloride at 110° C. for one hour. After cooling, thereaction mixture is stirred with water and dichloromethane, withice-cooling. The organic phase is separated off, dried and concentratedunder reduced pressure. The residue is chromatographed on silica gelusing methyl t-butyl ether/petroleum ether (1:9). This gives 5 g (16.4%of theory) of3,5,7-trichloro-6-(2,4,6-trifluorophenyl)pyrazolo[1,5-a]pyrimidine.

HPLC: log P=3.97

Example 443

Process (d):

14.2 g (11.9 mmol) of 25% pure3-chloro-6-(2-chloro-4-fluorophenyl)pyrazolo[1,5-a]pyrimidin-7-ol and1.24 g (5.9 mmol) of phosphorus pentachloride are stirred in 16.3 g ofphosphorus oxychloride at 110° C. for one hour and then for4 hourswithout further heating. After cooling, the reaction mixture is stirredwith water and dichloromethane, with ice-cooling. The organic phase isseparated off, dried and concentrated under reduced pressure. Theresidue is chromatographed on silica gel using n-hexane/ethyl acetate(3:1 to 1:1). This gives 2.1 g (54% of theory) of3,7-dichloro-6-(2-chloro-4-fluorophenyl)pyrazolo[1,5-a]pyrimidine.

HPLC: log P=3.56

The compounds of the formula

listed in Table 2 below are prepared by the methods described above.TABLE 2 Ex. No. X¹ Y¹ R³ X² logP m.p.: (° C.) 444 —Cl —Cl2-chloro-6-fluorophenyl —CN 3.31 445 —Cl —Cl 2-chloro-4-fluorophenyl —Cl446 —Cl —Cl 2,4-difluorophenyl —CN 3.16 136-38 447 —Cl —Cl2,6-dichlorophenyl —CN 3.59 448 —Cl —Cl 2,4,6-trifluorophenyl —CN 3.2449 —H —Cl 2-chloro-6-fluorophenyl —CN 450 H —Cl 2-chloro-6-fluorophenyl—Cl 451 —Cl —Cl 2,4,6-trifluorophenyl

4.38 452 —Cl —Cl 2-chlorophenyl

The logP values were determined in accordance with EEC Directive 79/831Annex V.A8 by HPLC (gradient method, acetonitrile/0.1% aqueousphosphoric acid)

Preparation of Intermediates of the Formulae (V) and (VI) Example 453

Process (f)

11.3 g (43.85 mmol) of methyl2-(2-chloro-4-fluorophenyl)-3-(dimethylamino)-2-acrylate and 5.2 g(43.85 mmol) of 4-chloro-1H-pyrazole-5-amine are stirred in 11.5 ml oftri-n-butylamine at 180° C. for 6 hours, and the methanol anddimethylamine formed are distilled off. The mixture is then concentratedfurther under reduced pressure. This gives 14.2 g (27% of theory) of 25%pure 3-chloro-6-(2-chloro-4-fluorophenyl)pyrazolo[1,5-a]pyrimidin-7-ol.

Example 454

Process (g)

11.15 g (42.5 mmol) of dimethyl 2-(2,4,6-trifluorophenyl)malonate and 5g (42.5 mmol) of 4-chloro-1H-pyrazole-5-amine are stirred in 11.5 ml oftri-n-butylamine at 180° C. for 3 hours, and the methanol formed isdistilled off. The product is decanted off. This gives 21 g (76% oftheory) of 49% pure3-chloro-6-(2,4,6-trifluorophenyl)pyrazolo[1,5-a]pyrimidine-5,7-diol.

The compounds of the formula

listed in Table 3 below are also prepared by the methods describedabove. TABLE 3 Ex. No. R³ X³ log P 455 2,4,6-trifluorophenyl

456 2-chlorophenyl

457 2-chloro-4-fluorophenyl —CH₃

Preparation of Amines of the Formula (III) Example 458

Process (h), First Step:

1000 mg of ethyl N-methoxycarbamate are initially charged in 10.0 ml ofdimethylformamide and 403 mg of sodium hydride are added a little at atime and the temperature was maintained by cooling at 30° C. Thereaction mixture is stirred at 30° C. for 2 hours, and 3500 mg of2-bromoethyl methyl ether are then added. The reaction mixture isstirred at 20° C.-25° C. for 18 hours and then stirred into 20 ml ofwater. The resulting reaction mixture is concentrated to dryness underreduced pressure and extracted four times with in each case 30 ml ofdichloromethane. The organic extracts are dried over sodium sulphate,filtered and concentrated to dryness under reduced pressure.

This gives 1200 mg of ethyl (N-methoxy-N-methoxyethyl)carbamate (purity77.6%, yield 62.6%).Process (h), Second Step:

200 mg of ethyl (N-methoxy-N-methoxyethyl)carbamate are initiallycharged in 4.0 ml of aqueous ethanol (59%), 240.6 mg of potassiumhydroxide are added and the mixture is stirred at 40° C. for 18 hours.The reaction mixture is then stirred into 50 ml of water and extractedthree times with in each case 20 ml of diethyl ether and three timeswith in each case 20 ml of dichloromethane. The combined organic phasesare washed twice with in each case 20 ml of water, dried and, at 20° C.and under reduced pressure, concentrated to a volume of 20 ml.

With ice-cooling, 2 ml of hydrochloric acid are added to the resultingsolution and the mixture is stirred at room temperature for 1 hour and,at 20° C. and under reduced pressure, concentrated to dryness.

The resulting product is digested three times with in each case 15 ml ofmethanol and then, at 20° C. and under reduced pressure, concentrated todryness.

This gives 140 mg of N-methoxy-N-methoxyethylamine hydrochloride (yield87.6%).

Example 459

Process (i), First Step:

A mixture of 1000 mg of ethyl N-hydroxy-N-methylcarbamate and 1166 mg of2-bromoethyl methyl ether is heated with stirring to reflux temperature,and a solution of 493 mg of potassium hydroxide in 5 ml of ethanol isthen added dropwise. The reaction mixture is boiled under reflux for 10hours and then worked up by filtering the reaction mixture andconcentrating the filtrate under reduced pressure. A mixture of waterand ethyl acetate is added to the residue that remains. The organicphase is separated off and washed with saturated aqueous ammoniumchloride solution and then with water. The organic phase is then driedover sodium sulphate and concentrated under reduced pressure. This gives0.7 g of a product which, according to gas chromatography, consists to83% of ethyl (N-methyl-N-methoxyethoxy)carbamate. Accordingly, thecalculated yield is 39% of theory.Process (i), Second Step:

240.6 mg of powdered potassium hydroxide are added to a mixture of 200mg of ethyl(N-methyl-N-methoxyethoxy)carbamate, 4 ml of ethanol and 4 mlof water, and the mixture is stirred at 40° C. for 2 hours. The reactionmixture is then stirred into 50 ml of water, and then extracted threetimes with in each case 20 ml of diethyl ether and subsequently threetimes with in each case 20 ml of methylene chloride. The combinedorganic phases are washed twice with in each case 20 ml of water, driedover sodium sulphate and, at room temperature and under reducedpressure, concentrated to a volume of 20 ml. With ice-cooling, 1 ml ofethereal hydrochloric acid is added to the resulting solution. Thecrystals that precipitate out are filtered off and dried. In thismanner, 190 mg of N-methyl-N-methoxyethoxyamine hydrochloride areobtained.

Example 460

Process (i), First Step:

At room temperature and with stirring, 475 mg of sodium hydride areadded to a mixture of 2000 mg of ethylN-(2,2,2-trifluoro-1-methylethyl)carbamate and 20 ml of tetrahydrofuran.A solution of 4600 mg of iodomethane in 10 ml of tetrahydrofuran is thenadded dropwise with stirring and at room temperature. The reactionmixture is stirred at 50° C. for 16 hours, and water is then added. Themixture is extracted three times with in each case 20 ml of methylenechloride and the combined organic phases are dried over sodium sulphateand concentrated under reduced pressure. This gives 1000 mg of a productwhich, according to gas chromatography, consists to 75% of ethylN-(2,2,2-trifluoro-1-methylethyl)-N-methylcarbamate. Accordingly, thecalculated yield is 34.86%.Process (j), Second Step:

1070 mg of powdered potassium hydroxide are added to a mixture of 1000mg of ethyl N-(2,2,2-trifluoro-1-methylethyl)-N-methylcarbamate, 20 mlof ethanol and 20 ml of water, and the mixture is stirred at 40° C. for66 hours. The reaction mixture is then diluted with water and extractedthree times with in each case 20 ml of a mixture of identical parts ofmethylene chloride and diethyl ether. The combined organic phases aredried over sodium sulphate and then concentrated at room temperature andunder slightly reduced pressure. With ice-cooling, ethereal hydrochloricacid is added to the resulting solution and the mixture is stirred atroom temperature for 60 hours. Concentration under reduced pressuregives 280 mg of N-(2,2,2-trifluoro-1-methylethyl)-N-methylaminehydrochloride. Accordingly, the calculated yield is 34% of theory.

Example 461

Process (k):

600 mg of benzyl N-(1-trifluoromethyl-2-propene)carbamate in 8.0 ml of16% strength hydrochloric acid are heated under reflux for 1.5 hours.After cooling to 20° C., the mixture is extracted twice with in eachcase 20 ml of diethyl ether.

The aqueous phase that remains is concentrated to dryness under reducedpressure and three portions of in each case 10 ml of methanol are added.The methanol is removed under reduced pressure and 310 mg of(1-trifluoromethylprop-2-ene)amine hydrochloride are isolated.Accordingly, the calculated yield is 82.9% of theory.

The carbamates listed in the tables below can also be prepared by themethods described above. TABLE 4 (XII)

Example No. Comp. No. R⁷ logP 462 XII-2

2.38 463 XII-3

2.06

TABLE 5 (XIV)

Example No. Comp. No. R⁷ Physical const. 464 XIV-2

TABLE 6 (XVII)

Example Comp. No. No. R⁸ Physical const. 465 XVII-2 —C₂H₅ ¹H-NMR (400MHz, CD₃CN): δ (ppm) = 1.13 (t, CH₃CH₂N), 1.21 (t, CH₃CHCF₃), 1.23 (t,CH₃CH₂O), 3.20 (m, CH₂N, CHCF₃), 4.1 (q, CH₃CH₂O).

The amines listed below can also be prepared by the methods describedabove. TABLE 7 (III)

Example Comp. No. No. R¹ R² Physical const. 466 III-5

—OCH₃ ¹H-NMR (400 MHz, CD₃CN): δ (ppm) = 1.03 (d, CH₃)₂CH), 3.06 (d,CH₂), 3.28 (b, (CH₃)₂CH), 4.01 (s, OCH₃) 467 III-6

—OCH₃ ¹H-NMR (400 MHz, DMSO): δ (ppm) = 1.76 (s, CH₃(CCH₂)CH₂), 3.29 (b,NH, CH₃(CCH₂)CH₂, OCH₃), 7.89, 5.02 (2 s, CH₃(CCH₂)CH₂). 468 III-7

469 III-8

—C₂H₅ ¹H-NMR (400 MHz, DMSO): δ (ppm) = 1.06 (m, CH₃CH₂N, CH₃CHCF₃),3.20 (m, CH₂N), 4.1 (m, CHCF₃).

The amines listed in Examples 466 to 469 were in each case isolated andterized in the form of their hydrochlorides.

Preparation of an Aminopyrazole Example 470

a) Under an atmosphere of argon and with stirring at room temperature,400 ml of diethyl ether are added dropwise over a period of one hour toa mixture of 16.223 g (200 mmol) of cyclopropylacetonitrile and 15.556 g(210 mmol) of ethyl formate. 4.598 g (200 mmol) of sodium are added, andthe mixture is stirred at room temperature for 4 days. Once the metallicsodium has dissolved, the mixture is cooled to 10° C. and 12.01 g (200mmol) of acetic acid are added over a period of 30 minutes, the reactionmixture being maintained at temperatures between 10° C. and 15° C. Thereaction mixture is stirred for another 15 minutes and then filtered offwith suction, and the residue is washed with 30 ml of cold diethylether. The filtrate is concentrated under reduced pressure. This gives22.0 g of 1-formyl-1-cyclopropylacetonitrile in the form of a crudeproduct which is used without prior purification for the furthersynthesis.

b) With stirring at room temperature, a mixture of 8.670 g (0.173 mol)of hydrazine hydrate and 3.12 ml of acetic acid is introduced into asolution of 21.825 g (0.200 mol) of 1-formyl-1-cyclopropylacetonitrilein 20 ml of ethanol. The reaction mixture is stirred under reflux for 4hours and then worked up by concentration under reduced pressure. Thisgives 13.7 g (55.6% of theory) of 4-cyclopropyl-1H-pyrazole-5-amine.

Use Examples Example A

Venturia Test (Apple)/Protective Solvents: 24.5 parts by weight ofacetone 24.5 parts by weight of dimethylacetamide Emulsifier:  1.0 partby weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated application rate. After thespray coating has dried on, the plants are inoculated with an aqueousconidia suspension of the apple scab pathogen Venturia inaequalis andthen remain in an incubation cabin at about 20° C. and 100% relativeatmospheric humidity for 1 day.

The plants are then placed in a greenhouse at about 21° C. and arelative atmospheric humidity of about 90%.

Evaluation is carried out 10 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

Active compounds, active compound application rates and test results areshown in the table below. TABLE A Venturia test (apple)/protectiveApplication rate Efficacy Active compound in g/ha in % According to theinvention:

100

100 97

100 100

100 100

100 100

100 98

100 100

100 100

100 100

100 98

100 100

100 100

100 93

100 100

100 100

100 99

100 98

100 99

100 100

100 100

Example B

Botrytis Test (Bean)/Protective Solvents: 24.5 parts by weight ofacetone 24.5 parts by weight of dimethylacetamide Emulsifier:  1.0 partby weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration. To test for protective activity, young plants are sprayedwith the preparation of active compound at the stated application rate.After the spray coating has dried on, 2 small pieces of agar colonizedby Botrytis cinerea are placed onto each leaf. The inoculated plants areplaced in a dark chamber at about 20° C. and 100% relative atmospherichumidity.

2 days after the inoculation, the size of the infected areas on theleaves is evaluated. 0% means an efficacy which corresponds to that ofthe control, whereas an efficacy of 100% means that no infection isobserved.

Active compounds, active compound application rates and test results areshown in the table below. TABLE B Botrytis test (bean)/protective Activecompound application rate Efficacy Active compound in g/ha in %According to the invention:

500 93

500 96

500 99

500 100

500 99

500 100

500 95

500 96

500 97

500 93

500 100

500 100

500 99

500 100

500 100

500 95

500 94

500 99

500 100

500 100

Example C

Altemaria Test (Tomato)/Protective Solvent: 49 parts by weight ofN,N-dimethylformamide Emulsifier:  1 part by weight of alkylarylpolyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young tomato plants are sprayed withthe preparation of active compound at the stated application rate. 1 dayafter the treatment, the plants are inoculated with a spore suspensionof Alternaria solani and then remain at 100% rel. humidity and 20° C.for 24 h. The plants then remain at 96% rel. atmospheric humidity and atemperature of 20° C.

Evaluation is carried out 7 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

Active compounds, active compound application rates and test results areshown in the table below. TABLE C Alternaria test (tomato)/protectiveActive compound application rate Efficacy Active compound in g/ha in %According to the invention:

750 95

750 95

750 95

750 95

750 95

750 90

Example D

Fusarium nivale (var. majus) Test (Wheat)/Protective Solvent:  25 partsby weight of N,N-dimethylacetamide Emulsifier: 0.6 part by weight ofalkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated application rate. After thespray coating has dried on, the plants are sprayed with a conidiasuspension of Fusarium nivale (var. majus).

The plants are placed in a greenhouse under transparent incubation hoodsat a temperature of about 15° C. and a relative atmospheric humidity ofabout 100%.

Evaluation is carried out 6 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

Active compounds, active compound application rates and test results areshown in the table below. TABLE D Fusarium nivale (var. majus) test(wheat)/protective Active compound application rates Efficacy Activecompound in g/ha in % According to the invention:

500 88

500 100

500 80

Example E

Pyricularia Test (Rice)/Protective Solvent:  25 parts by weight ofN,N-dimethylacetamide Emulsifier: 0.6 part by weight of alkylarylpolyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, and theconcentrate is diluted with water and the stated amount of emulsifier tothe desired concentration.

To test for protective activity, young rice plants are sprayed with thepreparation of active compound at the stated application rate. After thespray coating has dried on, the plants are inoculated with an aqueousspore suspension of Pyricularia oryzae. The plants are then placed in agreenhouse at 100% relative atmospheric humidity and 25° C.

Evaluation is carried out 6 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

Active compounds, active compound application rates and test results areshown in the table below. TABLE E Pyricularia test (rice)/protectiveActive compound application rate Efficacy Active compound in g/ha in %According to the invention:

500 88

500 88

500 86

500 75

Example F

Plutella Test Solvent:  100 parts by weight of acetone 1900 parts byweight of methanol

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, and theconcentrate is diluted with methanol to the desired concentrations.

A stated amount of preparation of active compound of the desiredconcentration is pipetted onto a standardized amount of synthetic feed.After the methanol has evaporated, about 200-300 eggs of the diamondbackmoth (Plutella xyostella) are placed onto the feed.

After the desired period of time, the kill of the eggs or larvae in % isdetermined. 100% means that all animals have been killed; 0% means thatnone of the animals has been killed.

Active compounds, active compound concentrations and test results areshown in the table below. TABLE F Plant-damaging insects Plutella testConcentration of active compound Kill rate in Active compound in ppm %after 7^(d) According to the invention:

1000 100

1-12. (canceled)
 13. A pyrazolopyrimidine of formula (I)

in which R¹ represents amino or hydroxyl; or represents optionallysubstituted alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, alkenyloxy,alkynyloxy, cycloalkyloxy, alkylamino, dialkylamino, alkenylamino,alkynylamino, cycloalkylamino, N-cycloalkyl-N-alkylamino,alkylideneamino, or heterocyclyl, R² represents hydrogen; or representsoptionally substituted alkyl, alkenyl, alkynyl, or cycloalkyl, or R¹ andR² together with the nitrogen atom to which they are attached form anoptionally substituted heterocyclic ring, R³ represents optionallysubstituted aryl, X¹ represents hydrogen or halogen, and X² representshalogen, cyano, nitro, alkyl, haloalkyl, cycloalkyl, formyl,thiocarbamoyl, alkoxycarbonyl, alkylcarbonyl, hydroximinoalkyl, oralkoximinoalkyl, with the proviso that when R¹ represents amino, thepyrazolopyrimidine of formula (I) is optionally in the form of an acidaddition salt. 14 A process for preparing pyrazolopyrimidines of formula(I) according to claim 13 comprising (a) reacting ahalopyrazolopyrimidine of formula (II)

in which R³ and X¹ are as defined for formula (I) in claim 13, x³represents halogen, cyano, nitro, alkyl, haloalkyl, cycloalkyl,thiocarbamoyl, alkoxycarbonyl, or alkylcarbonyl, and Y¹ representshalogen, with an amine of formula (III)

in which R¹ and R² are as defined for formula (I) in claim 13,optionally in the presence of a diluent, optionally in the presence of acatalyst, and optionally in the presence of an acid acceptor, or (b)reacting a pyrazolopyrimidine of formula (Ia)

in which R¹, R², R³, and X¹ are as defined for formula (I) in claim 13,with a diisobutylaluminum hydride in the presence of aqueous ammoniumchloride solution and in the presence of an organic diluent, or (c)reacting a pyrazolopyrimidine of formula (Ib)

in which R¹, R², R³, and X¹ are as defined for formula (I) in claim 13,with an amino compound of formula (IV)H₂N—OR⁴   (IV), or an acid addition salt thereof, in which R⁴ representshydrogen or alkyl, in the presence of a diluent and optionally in thepresence of a catalyst, and when R¹ represents amino, optionally addingan acid to the resulting pyrazolopyrimidine of formula (I).
 15. Acomposition for controlling harmful organisms comprising one or morepyrazolopyrimidines of formula (I) according to claim 13, or an acidaddition salt thereof, and one or more extenders and/or surfactants. 16.A method for controlling harmful organisms comprising applying aneffective amount of one or more pyrazolopyrimidines of formula (I)according to claim 13, or an acid addition salt thereof, the harmfulorganisms and/or their habitat.
 17. A process for preparing acomposition for controlling harmful organisms comprising mixing one ormore pyrazolopyrimidines of formula (I) according to claim 13, or anacid addition salt thereof, with one or more extenders and/orsurfactants.
 18. A halopyrazolopyrimidine of formula (II)

in which R³ represents optionally substituted aryl, X¹ representshydrogen or halogen, X¹ represents halogen, cyano, nitro, alkyl,thiocarbamoyl, cycloalkyl, haloalkyl, alkoxycarbonyl, or alkylcarbonyl,and Y¹ represents halogen.
 19. A process for preparing ahalopyrazolopyrimidine of formula (II) according to claim 18 comprising(d) reacting a hydroxypyrazolopyrimidine of formula (V)

in which R³ and X³ are as defined for formula (II) in claim 18, with ahalogenating agent, optionally in the presence of a diluent, or (e)reacting a dihydroxypyrazolopyrimidine of formula (VI)

in which R³ and X³ are as defined for formula (II) in claim 18, with ahalogenating agent, optionally in the presence of a diluent.
 20. Ahydroxypyrazolopyrimidine of formula (V)

in which R³ represents optionally substituted aryl, and X³ representshalogen, cyano, nitro, alkyl, thiocarbamoyl, cycloalkyl, haloalkyl,alkoxycarbonyl, or alkylcarbonyl.
 21. A process for preparing ahydroxypyrazolopyrimidine of formula (V) according to claim 20comprising (f) acrylic acid esters of the formula

in which R³ is as defined for formula (V) in claim 20, R⁵ representsalkyl, and Y² represents alkoxy or dialkylamino, with an aminopyrazoleof formula (VIII)

in which X³ is as defined for formula (V) in claim 20, optionally in thepresence of a diluent and optionally in the presence of a base.
 22. Adihydroxypyrazolopyrimidine of formula (VI)

in which R³ represents optionally substituted aryl, and X³ representshalogen, cyano, nitro, alkyl, thiocarbamoyl, cycloalkyl, haloalkyl,alkoxycarbonyl, or alkylcarbonyl.
 23. A process for preparing adihydroxypyrazolopyrimidine of formula (VI) according to claim 22comprising (g) reacting a malonic ester of formula (IX)

in which R³ is as defined for formula (VI) in claim 22, and R⁶represents alkyl, with an aminopyrazole of formula (VIII)

in which X³ is as defined for formula (VI) in claim 22, optionally inthe presence of a diluent and optionally in the presence of a strongbase.